TW201542746A - Die-bonding film, die-bonding film having a dicing sheet, semiconductor device, and manufacturing method for a semiconductor device - Google Patents
Die-bonding film, die-bonding film having a dicing sheet, semiconductor device, and manufacturing method for a semiconductor device Download PDFInfo
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Abstract
Description
本發明係關於黏晶薄膜、附有切割片之黏晶薄膜、半導體裝置、及半導體裝置之製造方法。 The present invention relates to a die-bonding film, a die-bonding film with a dicing sheet, a semiconductor device, and a method of manufacturing a semiconductor device.
以往，於半導體裝置之製造過程中有時使用黏晶薄膜(例如參照專利文獻1)。黏晶薄膜於將半導體晶片固定於引線框等被黏物時使用。 Conventionally, a die-bonding film has been used in the production process of a semiconductor device (see, for example, Patent Document 1). The die-bonding film is used when the semiconductor wafer is fixed to an adherend such as a lead frame.
[專利文獻1]日本特開平05-179211號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 05-179211
但是，黏晶薄膜中，於將附有黏晶薄膜之半導體晶片於引線框等上進行黏晶時，具有於黏晶薄膜與半導體晶片之間或黏晶薄膜與被黏物之間產生氣泡(空隙) 之問題。 However, in the die-bonding film, when the semiconductor wafer with the die-bonded film is bonded to a lead frame or the like, bubbles are formed between the die-bonded film and the semiconductor wafer or between the die-bonded film and the adherend ( Void) The problem.
本發明係有鑒於前述問題而進行，其目之在於提供即使在黏晶薄膜與半導體晶片之間或黏晶薄膜與被黏物之間產生空隙，也可降低空隙之影響之黏晶薄膜、及附有切割片之黏晶薄膜。另外在於提供使用該黏晶薄膜、或該附有切割片之黏晶薄膜而製造之半導體裝置。另外在於提供使用該附有切割片之黏晶薄膜之半導體裝置之製造方法。 The present invention has been made in view of the above problems, and an object thereof is to provide a die-bonding film which can reduce the influence of voids even when a void is formed between a die-bonding film and a semiconductor wafer or between a die-bonding film and an adherend, and A die-bonded film with a dicing sheet. Further, a semiconductor device manufactured using the die-bonded film or the die-bonded film with the dicing sheet is provided. Further, a method of manufacturing a semiconductor device using the dicing film-attached microcrystalline film is provided.
本發明人為了解決前述問題，進行了深入研究。結果發現，經由採用下述構成之黏晶薄膜，由此即使於黏晶薄膜與半導體晶片之間或黏晶薄膜與被黏物之間產生空隙，也可降低空隙之影響，並且完成了本發明。 The inventors conducted intensive studies in order to solve the aforementioned problems. As a result, it has been found that the effect of the void can be reduced even if a void is formed between the die-bonded film and the semiconductor wafer or between the die-bonded film and the adherend, and the present invention is completed. .
即，關於本發明之黏晶薄膜，其特徵在於，加熱處理前於150℃下之儲存彈性模量E’1為0.1MPa~10MPa，前述E’1與於150℃下加熱1小時後於150℃下之儲存彈性模量E’2之差即E’2-E’1為5MPa以下。 That is, the die-bonded film of the present invention is characterized in that the storage elastic modulus E'1 at 150 ° C before the heat treatment is 0.1 MPa to 10 MPa, and the above E'1 is heated at 150 ° C for 1 hour and then at 150 MPa. The difference in storage elastic modulus E'2 at °C, that is, E'2-E'1 is 5 MPa or less.
根據前述構成，加熱處理前於150℃下之儲存彈性模量E’1為10MPa以下，比較具有柔軟性。因此，即使於黏晶步驟中產生空隙，也可以利用密封步驟(利用密封樹脂密封半導體晶片之步驟)中之壓力，使該空隙在不發生膨脹之情況下分散在樹脂中，從而使其在視覺上消 失。結果，可降低空隙之影響。 According to the above configuration, the storage elastic modulus E'1 at 150 ° C before the heat treatment is 10 MPa or less, and is relatively flexible. Therefore, even if a void is generated in the die bonding step, the pressure in the sealing step (the step of sealing the semiconductor wafer with the sealing resin) can be utilized to disperse the void in the resin without being expanded, thereby making it visually Shangxiao Lost. As a result, the influence of the voids can be reduced.
另外，前述E’1與於150℃下加熱1小時後於150℃下之儲存彈性模量E’2之差(E’2-E’1)為5MPa以下，具有不易因密封步驟前之熱歷程而變硬之性質。因此，即使在經歷晶片之多段化等所致之長熱歷程後，也可經由密封步驟中之壓力使空隙於視覺上消失。結果，可降低空隙之影響。 Further, the difference (E'2-E'1) between the above E'1 and the storage elastic modulus E'2 at 150 ° C after heating at 150 ° C for 5 hours is 5 MPa or less, and it is difficult to heat due to the sealing step. The nature of the process and hardening. Therefore, even after a long thermal history due to the multi-stage of the wafer or the like, the void can be visually disappeared by the pressure in the sealing step. As a result, the influence of the voids can be reduced.
另外，加熱處理前於150℃下之儲存彈性模量E’1為0.1MPa以上，因此可防止引線接合時之晶片破裂。 Further, the storage elastic modulus E'1 at 150 ° C before the heat treatment is 0.1 MPa or more, so that cracking of the wafer at the time of wire bonding can be prevented.
前述構成中，前述E’1與前述E’2之比(E’1/E’2)為0.2~1為佳。 In the above configuration, the ratio (E'1/E'2) of the above E'1 to the above E'2 is preferably 0.2 to 1.
若前述比(E’1/E’2)為0.2以上，則具有不易因密封步驟前之熱歷程而變硬之性質。因此，即使在經歷晶片之多段化等所致之長之熱歷程後，也可經由密封步驟中之壓力使空隙在視覺上消失。結果，可進一步降低空隙之影響。 When the ratio (E'1/E'2) is 0.2 or more, it has a property that it is hard to be hardened by the heat history before the sealing step. Therefore, even after a long thermal history due to the multi-stage of the wafer or the like, the void can be visually disappeared via the pressure in the sealing step. As a result, the influence of the voids can be further reduced.
前述構成中，加熱處理前於150℃下之損失彈性模量E”1與於150℃下加熱1小時後於150℃下之損失彈性模量E”2之差(E”2-E”1)為1MPa以下，前述E”1與前述E”2之比(E”1/E”2)為0.2~1為佳。 In the above configuration, the difference between the loss elastic modulus E"1 at 150 ° C before the heat treatment and the loss elastic modulus E" 2 at 150 ° C after heating at 150 ° C for 1 hour (E"2-E"1 When it is 1 MPa or less, the ratio (E"1/E"2) of the above E"1 to the above E"2 is preferably 0.2 to 1.
若前述差(E”2-E”1)為1MPa以下，且前述比(E”1/E”2)為0.2以上，則具有不易因密封步驟前之熱歷程而變得更硬之性質。因此，即使在經歷晶片之多段 化等所致之長之熱歷程後，也可利用密封步驟中之壓力使空隙於視覺上消失。結果，可進一步降低空隙之影響。 When the difference (E"2-E"1) is 1 MPa or less and the ratio (E"1/E"2) is 0.2 or more, it has a property that it is hard to be hardened by the heat history before the sealing step. So even after experiencing multiple segments of the wafer After the long thermal history caused by the chemical, etc., the pressure in the sealing step can also be utilized to visually disappear the void. As a result, the influence of the voids can be further reduced.
前述構成中，加熱處理前之損耗角正切tanδ1之峰值溫度與於150℃下加熱1小時後之損耗角正切tanδ2之峰值溫度之差(tanδ2-tanδ1)為10℃以內為佳。 In the above configuration, the difference between the peak temperature of the loss tangent tan δ1 before the heat treatment and the peak temperature of the loss tangent tan δ2 after heating at 150 ° C for 1 hour (tan δ 2 - tan δ 1 ) is preferably 10 ° C or less.
若前述差(tanδ2-tanδ1)為10℃以內，則具有不易因密封步驟前之熱歷程而引起反應之性質。因此，即使在經歷晶片之多段化等所致之長之熱歷程後，也可保持具有柔軟性之狀態，也可利用密封步驟中之壓力使空隙在視覺上消失。結果，可進一步降低空隙之影響。 When the difference (tan δ 2 - tan δ 1) is within 10 ° C, it has a property that it is difficult to cause a reaction due to the heat history before the sealing step. Therefore, even after a long thermal history due to the multi-stage of the wafer or the like, the state of flexibility can be maintained, and the pressure in the sealing step can be used to visually disappear the void. As a result, the influence of the voids can be further reduced.
前述構成中，加熱處理前於25℃下之拉伸斷裂伸長率L1與在150℃下加熱1小時後於25℃下之拉伸斷裂伸長率L2之比(L2/L1)為0.5~1.0為佳。 In the above configuration, the ratio (L2/L1) of the tensile elongation at break L1 at 25 ° C before the heat treatment to the tensile elongation at break L2 at 25 ° C for 1 hour is 0.5 to 1.0. good.
若前述比(L2/L1)為0.5以上，則即使施加某種程度之熱，拉伸斷裂伸長率之變化也少。因此，具有不易因密封步驟前之熱歷程而引起反應之性質。因此，即使在經歷晶片之多段化等所致之長之熱歷程後，也可保持具有柔軟性之狀態，也可利用密封步驟中之壓力使空隙於視覺上消失。結果，可進一步降低空隙之影響。 When the ratio (L2/L1) is 0.5 or more, even if a certain amount of heat is applied, the change in tensile elongation at break is small. Therefore, it has a property that it is difficult to cause a reaction due to the heat history before the sealing step. Therefore, even after a long thermal history due to the multi-stage of the wafer or the like, the state of flexibility can be maintained, and the pressure in the sealing step can be used to visually disappear the void. As a result, the influence of the voids can be further reduced.
前述構成中，含有丙烯酸系共聚物，前述丙烯酸系共聚物經由將含有丙烯酸烷基酯或甲基丙烯酸烷基酯、與1重量%~30重量%之丙烯腈之單體原料聚合而得到，且具有環氧基或羧基作為官能基為佳。 In the above configuration, the acrylic copolymer is obtained by polymerizing a monomer raw material containing an alkyl acrylate or an alkyl methacrylate and 1% by weight to 30% by weight of acrylonitrile, and It is preferred to have an epoxy group or a carboxyl group as a functional group.
若含有具有作為官能基之環氧基、或羧基之 丙烯酸系共聚物，則可利用交聯形成步驟中之加熱經由前述官能基而形成交聯。另外，若前述丙烯酸系共聚物為經由將含有丙烯腈之單體原料聚合而得到之共聚物，則可提高交聯形成步驟中之凝聚力。結果，可提高交聯形成步驟後之接著力。 If it contains an epoxy group having a functional group, or a carboxyl group In the acrylic copolymer, crosslinking can be formed via the aforementioned functional groups by heating in the crosslinking forming step. Further, when the acrylic copolymer is a copolymer obtained by polymerizing a monomer raw material containing acrylonitrile, the cohesive force in the crosslinking formation step can be improved. As a result, the adhesion force after the crosslinking formation step can be improved.
前述構成中，實質上不含有熱交聯催化劑為佳。 In the above configuration, it is preferred that the thermally crosslinked catalyst is not substantially contained.
若實質上不含有熱交聯催化劑，則可抑制因密封步驟前之熱歷程而導致之交聯結構之形成。 If the thermal crosslinking catalyst is not substantially contained, the formation of the crosslinked structure due to the thermal history before the sealing step can be suppressed.
前述構成中，相對於全部有機樹脂組合物，含有0~15重量%之熱交聯劑為佳。 In the above configuration, it is preferred to contain 0 to 15% by weight of a thermal crosslinking agent based on the entire organic resin composition.
若相對於全部有機樹脂組合物，含有0~15重量%之熱交聯劑，則可利用交聯形成步驟中之加熱與熱可塑性樹脂所具有之官能基形成交聯結構。結果，可於交聯形成步驟中以抑制反應性之方式進行硬化。 When the thermal crosslinking agent is contained in an amount of from 0 to 15% by weight based on the entire organic resin composition, the crosslinking in the crosslinking forming step can form a crosslinked structure with the functional group of the thermoplastic resin. As a result, hardening can be performed in a cross-linking forming step in such a manner as to suppress reactivity.
前述構成中，前述熱交聯劑為選自環氧系熱交聯劑、酚系熱交聯劑、酸酐系熱交聯劑中之至少1種以上為佳。 In the above configuration, the thermal crosslinking agent is preferably at least one selected from the group consisting of an epoxy thermal crosslinking agent, a phenol thermal crosslinking agent, and an acid anhydride thermal crosslinking agent.
若前述熱交聯劑為選自環氧系熱交聯劑、酚系熱交聯劑、酸酐系熱交聯劑中之至少1種以上，則可得到高之凝聚力，可於回流焊評估中得到高之耐熱性。 When the thermal crosslinking agent is at least one selected from the group consisting of an epoxy thermal crosslinking agent, a phenol thermal crosslinking agent, and an acid anhydride thermal crosslinking agent, a high cohesive force can be obtained, which can be evaluated in reflow soldering. Get high heat resistance.
另外，關於本發明之附有切割片之黏晶薄膜之特徵在於，於切割片上設置有前述黏晶薄膜。 Further, the die-bonded film with a dicing sheet according to the present invention is characterized in that the above-mentioned viscous film is provided on the dicing sheet.
另外，關於本發明之半導體裝置之特徵在 於，使用前述之附有切割片之黏晶薄膜而製造。 In addition, the features of the semiconductor device of the present invention are Then, it is produced by using the above-mentioned microcrystalline film with a dicing sheet.
另外，關於本發明之半導體裝置之製造方法之特徵在於，包括：準備步驟，準備前述之附有切割片之黏晶薄膜、與貼合步驟，將前述附有切割片之黏晶薄膜之黏晶薄膜與半導體晶片之背面貼合、與切割步驟，將前述半導體晶片與前述黏晶薄膜一起切割，形成晶片狀之半導體晶片、與拾取步驟，將前述半導體晶片與前述黏晶薄膜一起從前述附有切割片之黏晶薄膜拾取、與晶片接合步驟，透過前述黏晶薄膜於被黏物上黏晶前述半導體晶片、與密封步驟，在前述黏晶步驟之後，利用密封樹脂將前述半導體晶片密封。 Further, a method of manufacturing a semiconductor device according to the present invention includes: a preparation step of preparing the above-mentioned die-bonding film with a dicing sheet, and a bonding step of laminating the above-mentioned dicing film with a dicing film The film is bonded to the back surface of the semiconductor wafer, and the dicing step is performed by cutting the semiconductor wafer together with the die-bonding film to form a wafer-shaped semiconductor wafer, and picking up the semiconductor wafer together with the die-bonding film. The die-bonding film of the dicing sheet is bonded to the wafer, and the semiconductor wafer is adhered to the adherend through the die-bonding film, and the sealing step is performed. After the die bonding step, the semiconductor wafer is sealed with a sealing resin.
根據前述構成，由於使用了前述附有切割片之黏晶薄膜，因此即使在黏晶步驟中產生空隙，也可以利用密封步驟中之壓力，使該空隙在不發生膨脹之情況下分散在樹脂中，從而使其在視覺上消失。結果，可降低空隙之影響。 According to the foregoing configuration, since the above-mentioned fused film having the dicing sheet is used, even if a void is generated in the die bonding step, the pressure in the sealing step can be utilized to disperse the void in the resin without expansion. So that it disappears visually. As a result, the influence of the voids can be reduced.
另外，前述E’1與於150℃下加熱1小時後於150℃下之儲存彈性模量E’2之差(E’2-E’1)為5MPa以下，具有不易因密封步驟前之熱歷程而變得更硬之性質。因此即使在經歷晶片之多段化等所致之長之熱歷程後，也可利用密封步驟中之壓力使空隙在視覺上消失。結果，可降低空 隙之影響。 Further, the difference (E'2-E'1) between the above E'1 and the storage elastic modulus E'2 at 150 ° C after heating at 150 ° C for 5 hours is 5 MPa or less, and it is difficult to heat due to the sealing step. The nature of the process has become harder. Therefore, even after a long thermal history due to the multi-stage of the wafer or the like, the pressure in the sealing step can be utilized to visually disappear the void. As a result, the space can be reduced The impact of the gap.
10‧‧‧附有切割片之黏晶薄膜 10‧‧‧Current film with dicing sheet
11‧‧‧切割片 11‧‧‧Cut slices
12‧‧‧基材 12‧‧‧Substrate
14‧‧‧黏著劑層 14‧‧‧Adhesive layer
16‧‧‧黏晶薄膜 16‧‧‧Met film
4‧‧‧半導體晶圓 4‧‧‧Semiconductor wafer
5‧‧‧半導體晶片 5‧‧‧Semiconductor wafer
6‧‧‧被黏物 6‧‧‧Adhesive
7‧‧‧引線接合 7‧‧‧ Wire bonding
8‧‧‧密封樹脂 8‧‧‧ Sealing resin
[圖1]係表示出關於本發明之一個實施方式之附有切割片之黏晶薄膜之剖面示意圖。 Fig. 1 is a schematic cross-sectional view showing a dicing film with a dicing sheet according to an embodiment of the present invention.
[圖2]係用於說明關於本實施方式之半導體裝置之一個製造方法之剖面示意圖。 FIG. 2 is a schematic cross-sectional view for explaining a manufacturing method of the semiconductor device of the present embodiment.
以下對於關於本發明之一個實施方式之黏晶薄膜、及附有切割片之黏晶薄膜進行說明。關於本實施方式之黏晶薄膜，可舉出以下說明之附有切割片之黏晶薄膜中未貼合切割片之狀態之黏晶薄膜。因此，以下中，對附有切割片之黏晶薄膜進行說明，在其中說明黏晶薄膜。圖1係表示出關於本發明之一個實施方式之附有切割片之黏晶薄膜之剖面示意圖。 Hereinafter, a die-bonding film according to an embodiment of the present invention and a die-bonding film with a dicing sheet will be described. The die-bonded film of the present embodiment may be a die-bonded film in a state in which the dicing sheet is not bonded to the dicing film having the dicing sheet described below. Therefore, in the following, a die-bonding film with a dicing sheet will be described, and a die-bonding film will be described. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a viscous film attached to a dicing sheet according to an embodiment of the present invention.
如圖1所示，附有切割片之黏晶薄膜10具有於切割片11上層合有黏晶薄膜16之構成。切割片11經由於基材12上層合黏著劑層14而構成，黏晶薄膜16設置在黏著劑層14上。 As shown in FIG. 1, the die-bonding film 10 with a dicing sheet has a structure in which a die-bonding film 16 is laminated on the dicing sheet 11. The dicing sheet 11 is formed by laminating the adhesive layer 14 on the substrate 12, and the die-bonding film 16 is provided on the adhesive layer 14.
又，本實施方式中，對切割片11存在未被黏 晶薄膜16覆蓋之部分14b之情況進行說明，但關於本發明之附有切割片之黏晶薄膜並不限定於該例，也可以以覆蓋整個切割片之方式於切割片層合黏晶薄膜。 Moreover, in the present embodiment, the dicing sheet 11 is not viscous. The case where the crystalline film 16 is covered with the portion 14b will be described. However, the die-bonded film with the dicing sheet of the present invention is not limited to this example, and the die-bonded film may be laminated to the dicing sheet so as to cover the entire dicing sheet.
黏晶薄膜16於加熱處理前於150℃下之儲存彈性模量E’1為0.1MPa~10MPa，0.2MPa~8MPa為佳，較佳為0.2MPa~5MPa。 The storage elastic modulus E'1 of the adhesive crystal film 16 at 150 ° C before the heat treatment is 0.1 MPa to 10 MPa, preferably 0.2 MPa to 8 MPa, preferably 0.2 MPa to 5 MPa.
另外，關於黏晶薄膜16，前述E’1與於150℃下加熱1小時後於150℃下之儲存彈性模量E’2之差(E’2-E’1)為5MPa以下，4MPa以下為佳，較佳為3MPa以下。 Further, regarding the die-bonding film 16, the difference (E'2-E'1) between the above-mentioned E'1 and the storage elastic modulus E'2 at 150 ° C after heating at 150 ° C for 1 hour is 5 MPa or less, 4 MPa or less. Preferably, it is preferably 3 MPa or less.
關於黏晶薄膜16，於加熱處理前於150℃下之儲存彈性模量E’1為10MPa以下，比較具有柔軟性。因此，即使於黏晶步驟中產生空隙，也可以利用密封步驟(利用密封樹脂密封半導體晶片之步驟)中之壓力，使該空隙在不發生膨脹之情況下分散於樹脂中，從而使其在視覺上消失。結果，可降低空隙之影響。 The storage elastic modulus E'1 at 150 ° C before the heat treatment is 10 MPa or less, and is relatively flexible. Therefore, even if a void is generated in the die bonding step, the pressure in the sealing step (the step of sealing the semiconductor wafer with the sealing resin) can be utilized to disperse the void in the resin without being expanded, thereby making it visually Disappeared. As a result, the influence of the voids can be reduced.
另外，關於黏晶薄膜16，前述差(E’2-E’1)為5MPa以下，具有不易因密封步驟前之熱歷程而變硬之性質。因此，即使在經歷晶片之多段化等所致之長之熱歷程後，也可利用密封步驟中之壓力使空隙在視覺上消失。結果，可降低空隙之影響。 Further, regarding the die-bonding film 16, the difference (E'2-E'1) is 5 MPa or less, and has a property that it is hard to be hardened by the heat history before the sealing step. Therefore, the void can be visually disappeared by the pressure in the sealing step even after a long thermal history due to the multi-stage of the wafer or the like. As a result, the influence of the voids can be reduced.
另外，關於黏晶薄膜16，加熱處理前於150℃下之儲存彈性模量E’1為0.1MPa以上，因此可防止引線接合時之晶片破裂。 Further, regarding the die-bonding film 16, the storage elastic modulus E'1 at 150 ° C before the heat treatment is 0.1 MPa or more, so that cracking of the wafer at the time of wire bonding can be prevented.
前述E’1及前述E’2可以經由構成黏晶薄膜16之材 料進行控制。例如，可以經由適當選擇構成黏晶薄膜16之熱可塑性樹脂之種類或含量，熱交聯劑之種類或含量來進行控制。 The above E'1 and the aforementioned E'2 may pass through the material constituting the die-bonding film 16. Control the material. For example, the type or content of the thermoplastic resin constituting the die-bonding film 16 and the type or content of the thermal crosslinking agent can be appropriately controlled.
關於黏晶薄膜16，前述E’1與前述E’2之比(E’1/E’2)0.2~1為佳，較佳為0.3~1.0，更佳為0.4~1.0。 Regarding the die-bonding film 16, the ratio (E'1/E'2) of the above E'1 to the above E'2 is preferably 0.2 to 1, preferably 0.3 to 1.0, more preferably 0.4 to 1.0.
若前述比(E’1/E’2)為0.2以上，則具有不易因密封步驟前之熱歷程而變得更硬之性質。因此，即使在經歷晶片之多段化等所致之長之熱歷程後，也可利用密封步驟中之壓力使空隙在視覺上消失。結果，可進一步降低空隙之影響。 When the ratio (E'1/E'2) is 0.2 or more, it has a property that it is hard to be hardened by the heat history before the sealing step. Therefore, the void can be visually disappeared by the pressure in the sealing step even after a long thermal history due to the multi-stage of the wafer or the like. As a result, the influence of the voids can be further reduced.
關於黏晶薄膜16，加熱處理前於150℃下之損失彈性模量E”1與在150℃下加熱1小時後於150℃下之損失彈性模量E”2之差(E”2-E”1)1MPa以下為佳，較佳為0.5MPa以下。 Regarding the difference between the loss elastic modulus E"1 at 150 ° C before the heat treatment, and the loss elastic modulus E" 2 at 150 ° C after heating at 150 ° C (E"2-E "1) is preferably 1 MPa or less, preferably 0.5 MPa or less.
另外，關於黏晶薄膜16，前述E”1與前述E”2之比(E”1/E”2)0.2~1為佳，較佳為0.3~1，更佳為0.4~1。 Further, regarding the die-bonding film 16, the ratio (E"1/E"2) of the above E"1 to the above E"2 is preferably 0.2 to 1, preferably 0.3 to 1, more preferably 0.4 to 1.
若黏晶薄膜16之前述差(E”2-E”1)為1MPa以下、並且前述比(E”1/E”2)為0.2以上，則具有不易因密封步驟前之熱歷程而變得更硬之性質。因此，即使在經歷晶片之多段化等所致之長之熱歷程後，也可利用密封步驟中之壓力使空隙在視覺上消失。結果，可進一步降低空隙之影響。 When the difference (E"2-E"1) of the adhesive film 16 is 1 MPa or less and the ratio (E"1/E"2) is 0.2 or more, it is difficult to become a heat history before the sealing step. Harder nature. Therefore, the void can be visually disappeared by the pressure in the sealing step even after a long thermal history due to the multi-stage of the wafer or the like. As a result, the influence of the voids can be further reduced.
前述E”1及前述E”2可以經由構成黏晶薄膜16之材 料進行控制。例如，可以經由適當選擇構成黏晶薄膜16之熱可塑性樹脂之種類或含量，熱交聯劑之種類或含量來進行控制。 The aforementioned E"1 and the aforementioned E"2 may pass through the material constituting the die-bonding film 16. Control the material. For example, the type or content of the thermoplastic resin constituting the die-bonding film 16 and the type or content of the thermal crosslinking agent can be appropriately controlled.
關於黏晶薄膜16，前述E”1(加熱處理前於150℃下之損失彈性模量E”1)0.01MPa~2MPa為佳，較佳為0.05MPa~1.5MPa，更佳為0.1MPa~1MPa。 Regarding the die-bonding film 16, the above E"1 (loss elastic modulus E at 150 °C before heat treatment) 1) is preferably 0.01 MPa to 2 MPa, preferably 0.05 MPa to 1.5 MPa, more preferably 0.1 MPa to 1 MPa. .
若黏晶薄膜16於加熱處理前於150℃下之損失彈性模量E”1為2MPa以下，則更具有柔軟性。因此，即使在黏晶步驟中產生空隙，也可以利用密封步驟(利用密封樹脂密封半導體晶片之步驟)中之壓力，使該空隙在不發生膨脹之情況下分散在樹脂中，從而使其在視覺上消失。結果，可進一步降低空隙之影響。 If the loss elastic modulus E"1 at 150 ° C before the heat treatment is 2 MPa or less, it is more flexible. Therefore, even if a void is generated in the die bonding step, a sealing step (using a seal can be utilized) The pressure in the step of sealing the semiconductor wafer with the resin causes the void to be dispersed in the resin without being expanded, thereby causing it to visually disappear. As a result, the influence of the void can be further reduced.
另外，若黏晶薄膜16於加熱處理前於150℃下之損失彈性模量E”1為0.01MPa以上，則可防止引線接合時之晶片破裂。 Further, if the loss elastic modulus E"1 at 150 ° C before the heat treatment is 0.01 MPa or more, the wafer can be prevented from being broken during wire bonding.
關於黏晶薄膜16，加熱處理前之損耗角正切tanδ1之峰值溫度與於150℃下加熱1小時後之損耗角正切tanδ2之峰值溫度之差(tanδ2-tanδ1)為10℃以內為佳，較佳為8℃以內，更佳為6℃以內。 Regarding the crystal film 16, the difference between the peak temperature of the loss tangent tan δ1 before the heat treatment and the peak temperature of the loss tangent tan δ2 after heating at 150 ° C for 1 hour (tan δ 2 - tan δ 1 ) is preferably 10 ° C or less, preferably. It is within 8 ° C, more preferably within 6 ° C.
若前述差(tanδ2-tanδ1)為10℃以內，則具有不易因密封步驟前之熱歷程而引起反應之性質。因此，即使在經歷晶片之多段化等所致之長之熱歷程後，也可保持具有柔軟性之狀態，也可利用密封步驟中之壓力使空隙在視覺上消失。結果，可進一步降低空隙之影響。 When the difference (tan δ 2 - tan δ 1) is within 10 ° C, it has a property that it is difficult to cause a reaction due to the heat history before the sealing step. Therefore, even after a long thermal history due to the multi-stage of the wafer or the like, the state of flexibility can be maintained, and the pressure in the sealing step can be used to visually disappear the void. As a result, the influence of the voids can be further reduced.
前述損耗角正切tanδ1之峰值溫度及損耗角正切tanδ2之峰值溫度可以經由構成黏晶薄膜16之材料進行控制。例如，可以經由適當選擇構成黏晶薄膜16之熱可塑性樹脂之種類或含量，熱交聯劑之種類或含量來進行控制。 The peak temperature of the loss tangent tan δ1 and the peak temperature of the loss tangent tan δ2 can be controlled by the material constituting the die-bonding film 16. For example, the type or content of the thermoplastic resin constituting the die-bonding film 16 and the type or content of the thermal crosslinking agent can be appropriately controlled.
關於黏晶薄膜16，加熱處理於在25℃下之拉伸斷裂伸長率L1與於150℃下加熱1小時後於25℃下之拉伸斷裂伸長率L2之比(L2/L1)為0.5~1.0為佳，較佳為為0.6~1.0，更佳為為0.7~1.0。 Regarding the die-bonding film 16, the ratio of the tensile elongation at break L1 at 25 ° C to the tensile elongation at break L2 at 25 ° C (L2/L1) after heating at 150 ° C for 1 hour is 0.5~. 1.0 is preferred, preferably 0.6 to 1.0, more preferably 0.7 to 1.0.
若前述比(L2/L1)為0.5以上，則即使施加某種程度之熱，拉伸斷裂伸長率之變化也少。因此，具有不易因密封步驟前之熱歷程而進一步引起反應之性質。因此，即使在經歷晶片之多段化等所致之長之熱歷程後，也可保持具有柔軟性之狀態，也可利用密封步驟中之壓力使空隙在視覺上消失。結果，可進一步降低空隙之影響。 When the ratio (L2/L1) is 0.5 or more, even if a certain amount of heat is applied, the change in tensile elongation at break is small. Therefore, it has a property that it is not easy to cause a reaction due to the heat history before the sealing step. Therefore, even after a long thermal history due to the multi-stage of the wafer or the like, the state of flexibility can be maintained, and the pressure in the sealing step can be used to visually disappear the void. As a result, the influence of the voids can be further reduced.
前述L1及前述L2可以經由構成黏晶薄膜16之材料進行控制。例如，可以經由適當選擇構成黏晶薄膜16之熱可塑性樹脂之種類或含量，熱交聯劑之種類或含量來進行控制。 The above L1 and the aforementioned L2 can be controlled via the material constituting the die-bonding film 16. For example, the type or content of the thermoplastic resin constituting the die-bonding film 16 and the type or content of the thermal crosslinking agent can be appropriately controlled.
黏晶薄膜16之前述L1為1500%以下為佳，較佳為1200%以下，更佳為1000%以下。若黏晶薄膜16之前述L1為1500%以下，則富有柔軟性，可利用密封步驟中之壓力使空隙在視覺上消失。拉伸斷裂伸長率之測定方法按照實施例記載之方法。 The L1 of the die-bonding film 16 is preferably 1500% or less, more preferably 1200% or less, still more preferably 1,000% or less. When the L1 of the die-bonding film 16 is 1500% or less, flexibility is obtained, and the void can be visually disappeared by the pressure in the sealing step. The method for measuring the tensile elongation at break is in accordance with the method described in the examples.
作為構成黏晶薄膜16之材料，可舉出熱可塑性樹脂。 The material constituting the die-bonding film 16 is a thermoplastic resin.
作為前述熱可塑性樹脂，可舉出：天然橡膠、丁基橡膠、異戊二烯橡膠、氯丁橡膠、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯樹脂、聚碳酸酯樹脂、熱可塑性聚醯亞胺樹脂、6-耐綸、6,6-耐綸等之聚醯胺樹脂、苯氧基樹脂、丙烯酸樹脂、PET或PBT等之飽和聚酯樹脂、聚醯胺醯亞胺樹脂或氟樹脂等。此等熱可塑性樹脂可以單獨使用，或者組合使用2種以上。此等之熱可塑性樹脂中，離子性雜質少、耐熱性高、可確保半導體晶片之可靠性之丙烯酸樹脂為佳。 Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and polybutylene. Saturated polycondensation of a diene resin, a polycarbonate resin, a thermoplastic polyimine resin, a polyamide resin such as 6-nylon, 6,6-nylon, a phenoxy resin, an acrylic resin, PET or PBT Ester resin, polyamidimide resin or fluororesin. These thermoplastic resins may be used singly or in combination of two or more. Among these thermoplastic resins, an acrylic resin having a small amount of ionic impurities and high heat resistance and ensuring the reliability of the semiconductor wafer is preferable.
作為前述丙烯酸類樹脂，沒有特別限定，可舉出以1種或2種以上具有碳數30以下、特別是碳數4~18之直鏈或支鏈烷基之丙烯酸之酯或甲基丙烯酸之酯(丙烯酸烷基酯、或甲基丙烯酸烷基酯)為成分之聚合物(丙烯酸類共聚物)等。作為前述烷基，可舉出例如：甲基、乙基、丙基、異丙基、正丁基、第三丁基、異丁基、戊基、異戊基、己基、庚基、環己基、2-乙基己基、辛基、異辛基、壬基、異壬基、癸基、異癸基、十一烷基、月桂基、十三烷基、十四烷基、硬脂基、十八烷基、或十二烷基等。 The acrylic resin is not particularly limited, and one or two or more kinds of esters of acrylic acid or methacrylic acid having a linear or branched alkyl group having a carbon number of 30 or less, particularly a carbon number of 4 to 18, may be mentioned. A polymer (acrylic copolymer) or the like having an ester (alkyl acrylate or alkyl methacrylate) as a component. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group or a cyclohexyl group. , 2-ethylhexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, Octadecyl or dodecyl and the like.
另外，作為形成前述聚合物之其他單體，沒有特別限制，可舉出例如：丙烯酸、甲基丙烯酸、丙烯酸 羧乙酯、丙烯酸羧戊酯、衣康酸、馬來酸、富馬酸或巴豆酸等之含羧基單體；馬來酸酐或衣康酸酐等之酸酐單體；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯或丙烯酸(4-羥基甲基環己基)甲酯等之含羥基單體；苯乙烯磺酸、烯丙磺酸、2-(甲基)丙烯醯胺基-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯或(甲基)丙烯醯氧基萘磺酸等之含磺酸基單體；丙烯醯磷酸-2-羥基乙酯等之含磷酸基單體、丙烯腈。 Further, the other monomer forming the polymer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, and acrylic acid. a carboxyl group-containing monomer such as carboxyethyl ester, carboxy amyl acrylate, itaconic acid, maleic acid, fumaric acid or crotonic acid; an anhydride monomer such as maleic anhydride or itaconic anhydride; (meth)acrylic acid 2- Hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, (A) a hydroxyl group-containing monomer such as 10-hydroxydecyl acrylate, 12-hydroxylauryl (meth)acrylate or (4-hydroxymethylcyclohexyl)methyl acrylate; styrene sulfonic acid, allyl sulfonic acid, 2 -(Methyl)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamide, propanesulfonic acid, sulfopropyl (meth)acrylate or (meth)acryloxynaphthalenesulfonic acid a sulfonic acid group-containing monomer; a phosphoric acid group-containing monomer such as acryloylphosphonium-2-hydroxyethyl ester; or acrylonitrile.
其中，關於黏晶薄膜16，含有丙烯酸系共聚物為佳，前述丙烯酸系共聚物經由將含有丙烯酸烷基酯或甲基丙烯酸烷基酯、與1重量%~30重量%之丙烯腈之單體原料聚合而得到，且具有環氧基或羧基作為官能基。前述單體原料中前述丙烯腈之含量較佳為5重量%~30重量%，更佳為7重量%~30重量%。若含有具有作為官能基之環氧基、或羧基之丙烯酸系共聚物，則可利用交聯形成步驟中之加熱經由前述官能基而形成交聯。另外，若前述丙烯酸系共聚物為經由將含有丙烯腈之單體原料聚合而得到之共聚物，則可提高交聯形成步驟中之凝聚力。結果，可提高交聯形成步驟後之接著力。另外，若前述丙烯酸系共聚物經由將含有丙烯酸烷基酯或甲基丙烯酸烷基酯之單體原料聚合而得到，則可賦予柔軟性。 In particular, the polycrystalline film 16 preferably contains an acrylic copolymer, and the acrylic copolymer contains a monomer containing acryl acrylate or alkyl methacrylate and 1% by weight to 30% by weight of acrylonitrile. The raw material is obtained by polymerization, and has an epoxy group or a carboxyl group as a functional group. The content of the acrylonitrile in the monomer raw material is preferably from 5% by weight to 30% by weight, more preferably from 7% by weight to 30% by weight. When an acrylic copolymer having an epoxy group or a carboxyl group as a functional group is contained, crosslinking can be formed by heating in the crosslinking formation step via the functional group. Further, when the acrylic copolymer is a copolymer obtained by polymerizing a monomer raw material containing acrylonitrile, the cohesive force in the crosslinking formation step can be improved. As a result, the adhesion force after the crosslinking formation step can be improved. Further, when the acrylic copolymer is obtained by polymerizing a monomer raw material containing an alkyl acrylate or an alkyl methacrylate, flexibility can be imparted.
在具有作為官能基之環氧基之情況下，從交聯後之柔軟性及耐熱性之觀點出發，環氧基之含有率為0.2eq/kg~1.0eq/kg為佳。 In the case of having an epoxy group as a functional group, the content of the epoxy group is preferably from 0.2 eq/kg to 1.0 eq/kg from the viewpoint of flexibility and heat resistance after crosslinking.
另外，在具有作為官能基之羧基之情況下，從交聯後之柔軟性及耐熱性之觀點出發，羧基之含有率為2mgKOH/g~50mgKOH/g為佳。 In addition, in the case of having a carboxyl group as a functional group, the carboxyl group content is preferably from 2 mgKOH/g to 50 mgKOH/g from the viewpoint of flexibility and heat resistance after crosslinking.
作為前述熱可塑性樹脂之摻合比例，沒有特別限定，但從賦予柔軟性之觀點出發，相對於全部有機樹脂組合物，為85重量%以上為佳，較佳為88重量%以上。另外，從賦予耐熱性之觀點出發，相對於全部有機樹脂組合物，為100重量%以下為佳，較佳為98重量%以下。 The blending ratio of the thermoplastic resin is not particularly limited. From the viewpoint of imparting flexibility, it is preferably 85% by weight or more, and preferably 88% by weight or more based on the total of the organic resin composition. In addition, from the viewpoint of imparting heat resistance, it is preferably 100% by weight or less, and preferably 98% by weight or less based on the total of the organic resin composition.
關於黏晶薄膜16，相對於全部有機樹脂組合物，含有0~15重量%之熱交聯劑為佳。相對於全部有機樹脂組合物，前述熱交聯劑之含量較佳為0~13重量%，更佳為0~11重量%。若黏晶薄膜16相對於全部有機樹脂組合物含有0~15重量%之熱交聯劑，則可利用交聯形成步驟中之加熱與熱可塑性樹脂所具有之官能基形成交聯結構。結果，可在交聯形成步驟中以抑制反應性之方式進行硬化。本說明書中，熱交聯劑係指，與熱可塑性樹脂所具有之官能基形成交聯結構之物質。 The adhesive film 16 preferably contains 0 to 15% by weight of a thermal crosslinking agent based on the entire organic resin composition. The content of the above thermal crosslinking agent is preferably from 0 to 13% by weight, more preferably from 0 to 11% by weight, based on the total of the organic resin composition. When the die-bonding film 16 contains 0 to 15% by weight of the thermal crosslinking agent with respect to the entire organic resin composition, the crosslinking in the crosslinking forming step can form a crosslinked structure with the functional group of the thermoplastic resin. As a result, hardening can be performed in a manner of suppressing reactivity in the crosslinking forming step. In the present specification, the thermal crosslinking agent means a substance which forms a crosslinked structure with a functional group possessed by the thermoplastic resin.
作為前述熱交聯劑之具體例，可舉出：環氧樹脂、酚醛清漆樹脂、酸酐。其中，於添加多種熱交聯劑之情況下，熱交聯劑以適合與熱可塑性樹脂所具有之官能 基形成交聯結構之方式進行選擇為佳，以熱交聯劑之間不發生反應之方式進行選擇為佳。若前述熱交聯劑為選自環氧系熱交聯劑、酚系熱交聯劑、酸酐系熱交聯劑中之至少1種以上，則可得到高之凝聚力，可在回流焊評估中得到高之耐熱性。 Specific examples of the thermal crosslinking agent include an epoxy resin, a novolak resin, and an acid anhydride. Wherein, in the case of adding a plurality of thermal crosslinking agents, the thermal crosslinking agent is suitable for the function of the thermoplastic resin It is preferred that the basis is formed in such a manner that the crosslinked structure is formed, and it is preferred to select in such a manner that no reaction occurs between the thermal crosslinking agents. When the thermal crosslinking agent is at least one selected from the group consisting of an epoxy thermal crosslinking agent, a phenol thermal crosslinking agent, and an acid anhydride thermal crosslinking agent, a high cohesive force can be obtained, which can be evaluated in reflow soldering. Get high heat resistance.
前述環氧樹脂沒有特別限制，可使用例如：雙酚A型、雙酚F型、雙酚S型、溴化雙酚A型、氫化雙酚A型、雙酚AF型、聯苯型、萘型、芴型、苯酚酚醛清漆型、鄰甲酚酚醛清漆型、三羥苯基甲烷型、四(羥苯基)乙烷型等之雙官能環氧樹脂或多官能環氧樹脂、或者乙內醯脲型、異氰脲酸三縮水甘油酯型或縮水甘油胺型等之環氧樹脂。它們可以單獨使用，或者組合使用2種以上。 The epoxy resin is not particularly limited, and for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene can be used. Type, bismuth, phenol novolak type, o-cresol novolak type, trishydroxyphenylmethane type, tetrakis (hydroxyphenyl) ethane type, etc., bifunctional epoxy resin or polyfunctional epoxy resin, or B An epoxy resin such as a guanidine type, an isocyanuric acid triglycidyl ester type or a glycidylamine type. They may be used alone or in combination of two or more.
前述酚醛清漆樹脂沒有特別限制，可舉出例如：苯酚酚醛清漆樹脂、苯酚芳烷基樹脂、甲酚酚醛清漆樹脂、第三丁基苯酚酚醛清漆樹脂、壬基苯酚酚醛清漆樹脂等之酚醛清漆型酚醛清漆樹脂、甲階酚醛清漆型酚醛清漆樹脂、聚對羥基苯乙烯等之聚羥基苯乙烯等。它們可以單獨使用，或者組合使用2種以上。 The novolak resin is not particularly limited, and examples thereof include a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a third butyl phenol novolak resin, and a nonylphenol novolak resin. A novolak resin, a resol novolak type novolac resin, a polyhydroxy styrene such as polyparaxyl styrene or the like. They may be used alone or in combination of two or more.
前述酸酐沒有特別限制，可舉出：鄰苯二甲酸酐、均苯四酸酐、偏苯三甲酸酐、馬來酸酐等。它們可以單獨使用，或者組合使用2種以上。 The acid anhydride is not particularly limited, and examples thereof include phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and maleic anhydride. They may be used alone or in combination of two or more.
另外，黏晶薄膜16中可以根據其用途適當配合填料。前述填料之摻合可賦予導電性、提高導熱性、調 節彈性模量等。作為前述填料，可舉出無機填料及有機填料，但從操作性之提高、熱導電性之提高、熔融黏度之調整、觸變性之賦予等特性之觀點出發，無機填料為佳。作為前述無機填料，沒有特別限制，可舉出例如，氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、硼酸鋁晶須、氮化硼、結晶二氧化矽、非晶二氧化矽等。它們可以單獨使用，也可以並用2種以上。從提高熱導電性之觀點出發，氧化鋁、氮化鋁、氮化硼、結晶二氧化矽、非晶二氧化矽為佳。另外，從上述各特性之平衡性高之觀點出發，結晶二氧化矽或非晶二氧化矽為佳。另外，為了實現導電性之賦予、熱導電性之提高等目之，作為無機填料，也可以使用導電性物質(導電填料)。 Further, the filler may be appropriately blended in the die-bonded film 16 depending on the use thereof. The blending of the foregoing fillers can impart conductivity, improve thermal conductivity, and adjust Sectional modulus of elasticity, etc. The inorganic filler and the organic filler are mentioned as the filler, but an inorganic filler is preferred from the viewpoints of improvement in workability, improvement in thermal conductivity, adjustment in melt viscosity, and imparting thixotropy. The inorganic filler is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, and boric acid. Aluminum whiskers, boron nitride, crystalline cerium oxide, amorphous cerium oxide, and the like. These may be used alone or in combination of two or more. From the viewpoint of improving thermal conductivity, alumina, aluminum nitride, boron nitride, crystalline cerium oxide, and amorphous cerium oxide are preferred. Further, from the viewpoint of high balance of the above characteristics, crystalline cerium oxide or amorphous cerium oxide is preferred. In addition, in order to achieve the imparting of conductivity and the improvement of thermal conductivity, a conductive material (conductive filler) may be used as the inorganic filler.
作為導電填料，可舉出：將銀、鋁、金、銅、鎳、導電性合金等製成球狀、針狀、薄片狀後之金屬粉、氧化鋁等金屬氧化物、無定形碳黑、石墨等。 Examples of the conductive filler include a metal powder such as silver, aluminum, gold, copper, nickel, or a conductive alloy which is formed into a spherical shape, a needle shape, or a flaky shape, a metal oxide such as alumina, or amorphous carbon black. Graphite, etc.
關於黏晶薄膜16，實質上不含有熱交聯催化劑為佳。實質上不含有熱交聯催化劑係指不含有、或者即使含有也相對於黏晶薄膜16整體以0.05重量%以下之量含有之情況。若黏晶薄膜16實質上不含有熱交聯催化劑，則可抑制因密封步驟前之熱歷程而導致之交聯結構之形成。 It is preferable that the die-bonding film 16 does not substantially contain a thermal crosslinking catalyst. The fact that the thermal cross-linking catalyst is not contained in the film is not contained or is contained in an amount of 0.05% by weight or less based on the entire thickness of the die-bonding film 16 . If the die-bonding film 16 does not substantially contain a thermal crosslinking catalyst, the formation of a crosslinked structure due to the heat history before the sealing step can be suppressed.
作為前述熱交聯催化劑，可使用例如：胺系熱交聯催化劑、磷系熱交聯催化劑、咪唑系熱交聯催化 劑、硼系熱交聯催化劑、磷-硼系熱交聯催化劑等。 As the thermal crosslinking catalyst, for example, an amine-based thermal crosslinking catalyst, a phosphorus-based thermal crosslinking catalyst, or an imidazole-based thermal crosslinking catalyst can be used. A catalyst, a boron-based thermal crosslinking catalyst, a phosphorus-boron-based thermal crosslinking catalyst, and the like.
作為前述胺系熱交聯催化劑，可舉出例如，單乙醇胺三氟硼酸鹽(stella-chemifa(股份有限公司)置)，雙氰胺(nacalai tesque(股份有限公司)製)等。 The amine-based thermal crosslinking catalyst may, for example, be monoethanolamine trifluoroborate (stella-chemifa (company)), dicyandiamide (manufactured by Nacalai tesque Co., Ltd.) or the like.
作為前述磷系熱交聯催化劑，可舉出例如，三苯基膦、三丁基膦、三(對甲基苯基)膦、三(壬基苯基)膦、二苯基甲苯基膦等之三有機膦；四苯基溴化鏻(商品名；TPP-PB)、甲基三苯基鏻(商品名；TPP-MB)、甲基三苯基氯化鏻(商品名；TPP-MC)、甲氧基甲基三苯基鏻(商品名；TPP-MOC)、苄基三苯基氯化鏻(商品名；TPP-ZC)等(均為北興化學(股份有限公司)製)。 Examples of the phosphorus-based thermal crosslinking catalyst include triphenylphosphine, tributylphosphine, tris(p-methylphenyl)phosphine, tris(nonylphenyl)phosphine, diphenyltolylphosphine, and the like. Triorganophosphine; tetraphenylphosphonium bromide (trade name; TPP-PB), methyltriphenylphosphonium (trade name; TPP-MB), methyltriphenylphosphonium chloride (trade name; TPP-MC) ), methoxymethyltriphenylphosphonium (trade name; TPP-MOC), benzyltriphenylphosphonium chloride (trade name; TPP-ZC), etc. (all manufactured by Beixing Chemical Co., Ltd.).
作為前述咪唑系熱交聯催化劑，可舉出：2-甲基咪唑(商品名；2MZ)、2-十一烷基咪唑(商品名；C11-Z)、2-十七烷基咪唑(商品名；C17Z)、1，2-二甲基咪唑(商品名；1.2DMZ)、2-乙基-4-甲基咪唑(商品名；2E4MZ)、2-苯基咪唑(商品名；2PZ)、2-苯基-4-甲基咪唑(商品名；2P4MZ)、1-苄基-2-甲基咪唑(商品名；1B2MZ)、1-苄基-2-苯基咪唑(商品名；1B2PZ)、1-氰基乙基-2-甲基咪唑(商品名；2MZ-CN)、1-氰基乙基-2-十一烷基咪唑(商品名；C11Z-CN)、1-氰基乙基-2-苯基咪唑鎓偏苯三酸鹽(商品名；2PZCNS-PW)、2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-均三嗪(商品名；2MZ-A)、2,4-二氨基-6-[2’-十一烷基咪唑基- (1’)]-乙基-均三嗪(商品名；C11Z-A)、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-均三嗪(商品名；2E4MZ-A)、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-均三嗪異氰脲酸加成物(商品名；2MA-OK)、2-苯基-4,5-二羥基甲基咪唑(商品名；2PHZ-PW)、2-苯基-4-甲基-5-羥基甲基咪唑(商品名；2P4MHZ-PW)等(均為四國化成工業(股份有限公司)製)。 Examples of the imidazole-based thermal crosslinking catalyst include 2-methylimidazole (trade name; 2MZ), 2-undecylimidazole (trade name; C11-Z), and 2-heptadecylimidazole (products). Name; C17Z), 1,2-dimethylimidazole (trade name; 1.2DMZ), 2-ethyl-4-methylimidazole (trade name; 2E4MZ), 2-phenylimidazole (trade name; 2PZ), 2-phenyl-4-methylimidazole (trade name; 2P4MZ), 1-benzyl-2-methylimidazole (trade name; 1B2MZ), 1-benzyl-2-phenylimidazole (trade name; 1B2PZ) , 1-cyanoethyl-2-methylimidazole (trade name; 2MZ-CN), 1-cyanoethyl-2-undecylimidazole (trade name; C11Z-CN), 1-cyanoethyl Benzyl-2-phenylimidazolium trimellitate (trade name; 2PZCNS-PW), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl- Triazine (trade name; 2MZ-A), 2,4-diamino-6-[2'-undecylimidazolyl- (1')]-ethyl-s-triazine (trade name; C11Z-A), 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1') ]-Ethyl-s-triazine (trade name; 2E4MZ-A), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanide Urea acid adduct (trade name; 2MA-OK), 2-phenyl-4,5-dihydroxymethylimidazole (trade name; 2PHZ-PW), 2-phenyl-4-methyl-5-hydroxyl Methyl imidazole (trade name; 2P4MHZ-PW), etc. (all manufactured by Shikoku Chemical Industry Co., Ltd.).
作為前述硼系熱交聯催化劑，沒有特別限制，可舉出例如三氯硼烷等。 The boron-based thermal crosslinking catalyst is not particularly limited, and examples thereof include trichloroborane.
作為前述磷-硼系熱交聯催化劑，沒有特別限制，可舉出例如，四苯基鏻四苯基硼酸鹽(商品名；TPP-K)，四苯基鏻四對甲苯基硼酸鹽(商品名；TPP-MK)，苄基三苯基鏻四苯基硼酸鹽(商品名；TPP-ZK)，三苯基膦三苯基硼烷(商品名；TPP-S)等(均為北興化學(股份有限公司)製)。 The phosphorus-boron-based thermal crosslinking catalyst is not particularly limited, and examples thereof include tetraphenylphosphonium tetraphenylborate (trade name; TPP-K) and tetraphenylphosphonium tetra-p-tolyl borate (product). Name; TPP-MK), benzyltriphenylphosphonium tetraphenylborate (trade name; TPP-ZK), triphenylphosphine triphenylborane (trade name; TPP-S), etc. (both Beixing Chemical (Company) system).
前述填料之平均粒徑為0.01~0.9μm為佳，較佳為0.05~0.7μm。經由使前述填料之平均粒徑為0.01μm以上，可確保黏晶薄膜之柔軟性。另外，經由使其為0.9μm以下，可防止填料從黏晶薄膜飛出。又，填料之平均粒徑例如為經由光度式之粒度分布計(HORIBA製，裝置名；LA-910)求出之值。 The average particle diameter of the filler is preferably 0.01 to 0.9 μm, preferably 0.05 to 0.7 μm. The softness of the die-bonded film can be ensured by setting the average particle diameter of the filler to 0.01 μm or more. Further, by making it 0.9 μm or less, it is possible to prevent the filler from flying out of the die-bonding film. Further, the average particle diameter of the filler is, for example, a value obtained by a photometric particle size distribution meter (manufactured by HORIBA, device name; LA-910).
作為前述填料之添加量，相對於黏晶薄膜16整體，0~80重量%為佳，較佳為0~60重量%。 The amount of the filler added is preferably from 0 to 80% by weight, preferably from 0 to 60% by weight, based on the entire thickness of the die-bonding film 16.
又，黏晶薄膜16中除前述填 料以外還可以根據根據需要適當摻合其他添加劑。其他添加劑作為，可舉出例如：阻燃劑、矽烷偶合劑或離子捕捉劑等。作為前述阻燃劑，可舉出例如：三氧化銻、五氧化銻、溴化環氧樹脂等。此等物質可以單獨使用或者兩種以上組合使用。作為前述矽烷偶合劑，可以列舉例如：β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷等。此等之化合物可以單獨使用或者兩種以上組合使用。作為前述離子捕捉劑，可以列舉水滑石類、氫氧化鉍等。此等物質可以單獨使用或者兩種以上組合使用。 Moreover, in the die-bonding film 16, in addition to the aforementioned filling In addition to the materials, other additives may be appropriately blended as needed. Examples of the other additives include a flame retardant, a decane coupling agent, and an ion scavenger. Examples of the flame retardant include antimony trioxide, antimony pentoxide, and brominated epoxy resin. These may be used singly or in combination of two or more. Examples of the decane coupling agent include β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, and γ-glycidoxy. Propylmethyldiethoxydecane, and the like. These compounds may be used singly or in combination of two or more. Examples of the ion trapping agent include hydrotalcites and barium hydroxide. These may be used singly or in combination of two or more.
黏晶薄膜16之厚度(在層合體之情況下為總厚度)沒有特別限定，5~100μm為佳，較佳為5~60μm，更佳為5~30μm。。 The thickness of the adhesive film 16 (the total thickness in the case of the laminate) is not particularly limited, and is preferably 5 to 100 μm, more preferably 5 to 60 μm, still more preferably 5 to 30 μm. .
如上所述，切割片11具有於基材12上層合有黏著劑層14之構成。 As described above, the dicing sheet 11 has a structure in which the adhesive layer 14 is laminated on the substrate 12.
基材12成為附有切割片之黏晶薄膜10之強度母體。可舉出例如：低密度聚乙烯、直鏈狀聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、聚丙烯無規共聚物、聚丙烯嵌段共聚物、聚丙烯均聚物、聚丁烯、聚甲基戊烯等之聚烯烴、乙烯-乙酸乙烯酯共聚物、離子聚物樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(無規、交替)共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物、聚氨酯、聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯等之聚酯、聚碳酸酯、聚醯亞胺、聚醚醚 酮、聚醚醯亞胺、聚醯胺、全芳香族聚醯胺、聚苯硫醚、芳族聚醯胺(紙)、玻璃、玻璃布、含氟樹脂、聚氯乙烯、聚偏二氯乙烯、纖維素系樹脂、聚矽氧烷樹脂、金屬(箔)等。基材12於後述之黏著劑層14由輻射線硬化型黏著劑形成之情況下，由透過該輻射線之材料形成為佳。 The substrate 12 becomes a strength matrix of the die-bonded film 10 to which the dicing sheet is attached. For example, low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, polypropylene random copolymer, polypropylene block copolymer, polypropylene homopolymerization Polyolefin, ethylene-vinyl acetate copolymer, ionic polymer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate (random) , alternating) copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, polyurethane, polyethylene terephthalate, polyethylene naphthalate, polyester, polycarbonate, poly Yttrium imine, polyether ether Ketones, polyether oximines, polyamines, wholly aromatic polyamines, polyphenylene sulfides, aromatic polyamides (paper), glass, glass cloth, fluororesin, polyvinyl chloride, polyvinylidene chloride Ethylene, cellulose resin, polysiloxane resin, metal (foil), and the like. When the adhesive layer 14 to be described later is formed of a radiation-curable adhesive, the substrate 12 is preferably formed of a material that transmits the radiation.
為了提高與鄰接層之密合性、保持性等，基材12之表面可以進行慣用之表面處理，例如鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、電離射線處理等之化學或物理處理、底塗劑(例如，後述之黏著物質)塗佈處理。前述基材12可以適當選擇使用同種或異種材料，根據需要也可以將多種材料混合使用。 In order to improve the adhesion to the adjacent layer, retention, etc., the surface of the substrate 12 can be subjected to conventional surface treatment such as chromic acid treatment, ozone exposure, flame exposure, high voltage electric shock exposure, ionizing radiation treatment, etc. A primer (for example, an adhesive substance to be described later) is applied. The substrate 12 may be appropriately selected from the same or different materials, and a plurality of materials may be used in combination as needed.
基材12之厚度可以沒有特別限制地適當確定，但一般為5~200μm左右。 The thickness of the substrate 12 can be appropriately determined without particular limitation, but is generally about 5 to 200 μm.
作為黏著劑層14之形成中使用之黏著劑，沒有特別限制，例如，可以使用丙烯酸系黏著劑、橡膠系黏著劑等一般之壓敏性黏著劑。作為前述壓敏性黏著劑，從半導體晶圓或玻璃等避忌污染之電子零件之、利用超純水或醇等之有機溶劑之清潔洗滌性等觀點出發，以丙烯酸系聚合物為基礎聚合物之丙烯酸系黏著劑為佳。 The adhesive used for the formation of the adhesive layer 14 is not particularly limited, and for example, a general pressure-sensitive adhesive such as an acrylic adhesive or a rubber-based adhesive can be used. The pressure-sensitive adhesive is an acrylic polymer-based polymer from the viewpoints of cleaning and washing properties of an organic solvent such as an ultrapure water or an alcohol, such as semiconductor wafers or glass, and the like. Acrylic adhesives are preferred.
作為前述丙烯酸系聚合物，可舉出例如使用(甲基)丙烯酸烷基酯(例如，甲酯、乙酯、丙酯、異丙酯、丁酯、異丁酯、第二丁酯、第三丁酯、戊酯、異戊酯、己酯、庚酯、辛酯、2-乙基己酯、異辛酯、壬酯、癸酯、異癸酯、十一烷基酯、十二烷基酯、十三烷基酯、十 四烷基酯、十六烷基酯、十八烷基酯、二十烷基酯等烷基之碳數1~30、特別是碳數4~18之直鏈狀或支鏈狀之烷基酯等)以及(甲基)丙烯酸環烷基酯(例如，環戊酯、環己酯等)中之一種或兩種以上作為單體成分之丙烯酸系聚合物等。又，(甲基)丙烯酸酯係指丙烯酸酯和/或甲基丙烯酸酯，本發明之(甲基)全部具有同樣之含義。 The acrylic polymer may, for example, be an alkyl (meth)acrylate (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, second butyl ester, or third). Butyl, pentyl, isoamyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, decyl, decyl, isodecyl, undecyl, dodecyl Ester, tridecyl ester, ten Alkyl group having a carbon number of 1 to 30, particularly a linear or branched alkyl group having 4 to 18 carbon atoms, such as a tetraalkyl ester, a hexadecyl ester, an octadecyl ester or an eicosyl ester. An acrylic polymer such as an ester or the like and a cycloalkyl (meth)acrylate (for example, a cyclopentyl ester or a cyclohexyl ester), or an acrylic polymer or the like as a monomer component. Further, (meth) acrylate means acrylate and/or methacrylate, and all (meth) of the present invention have the same meaning.
為了改善凝聚力、耐熱性等，前述丙烯酸系聚合物可以根據需要而含有可與前述(甲基)丙烯酸烷基酯或環烷基酯共聚之其他單體成分所對應之單元。作為這樣之單體成分，可以列舉例如：丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、衣康酸、馬來酸、富馬酸、巴豆酸等之含羧基單體；馬來酸酐、衣康酸酐等之酸酐單體；(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-4-羥基丁酯、(甲基)丙烯酸-6-羥基己酯、(甲基)丙烯酸-8-羥基辛酯、(甲基)丙烯酸-10-羥基癸酯、(甲基)丙烯酸-12-羥基月桂酯、(甲基)丙烯酸-(4-羥甲基環己基)甲酯等之含羥基單體；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等之含磺酸基單體；2-羥基乙基丙烯醯基磷酸酯等之含磷酸基單體；丙烯醯胺；丙烯腈等。此等可共聚單體成分可以使用一種或兩種以上。此等可共聚單體之使用量為全部單體成分之40重量%以下為佳。 In order to improve cohesive force, heat resistance, and the like, the acrylic polymer may contain a unit corresponding to another monomer component copolymerizable with the alkyl (meth)acrylate or the cycloalkyl ester, as needed. Examples of such a monomer component include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. a carboxyl group-containing monomer; an anhydride monomer such as maleic anhydride or itaconic anhydride; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid-4 -hydroxybutyl ester, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxyl (meth)acrylate a hydroxyl group-containing monomer such as lauryl ester or (meth)acrylic acid-(4-hydroxymethylcyclohexyl)methyl ester; styrenesulfonic acid, allylsulfonic acid, 2-(methyl)propenylamine-2- a sulfonic acid group-containing monomer such as methylpropanesulfonic acid, (meth)acrylamide, propanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloxynaphthalenesulfonic acid or the like; 2-hydroxyethyl a phosphoric acid group-containing monomer such as a acrylonitrile phosphate; acrylamide; acrylonitrile or the like. These copolymerizable monomer components may be used alone or in combination of two or more. The amount of these copolymerizable monomers used is preferably 40% by weight or less based on the total of the monomer components.
另外，為了進行交聯，前述丙烯酸系聚合物也可以根據需要含有多官能性單體等作為共聚用單體成分。作為這樣之多官能性單體，可舉出例如己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯等。此等之多官能性單體也可以使用一種或者兩種以上。從黏著特性等觀點出發，多官能性單體之使用量為全部單體成分之30重量%以下為佳。 In addition, the acrylic polymer may contain a polyfunctional monomer or the like as a monomer component for copolymerization as needed. Examples of such a polyfunctional monomer include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, and (poly)propylene glycol di(meth)acrylate. Neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(methyl) Acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, and the like. These polyfunctional monomers may be used alone or in combination of two or more. The amount of the polyfunctional monomer used is preferably 30% by weight or less based on the total monomer component from the viewpoint of adhesion characteristics and the like.
前述丙烯酸系聚合物可以經由將單一單體或者兩種以上單體混合物聚合而得到。聚合可以經由溶液聚合、乳化聚合、塊狀聚合、懸浮聚合等某種方式進行。從防止污染潔淨之被黏物等方面考慮，低分子量物質之含量小為佳。從該觀點出發，丙烯酸系聚合物之數平均分子量較佳為10萬以上，更佳20萬~300萬左右，特別佳為30萬~100萬左右。 The acrylic polymer can be obtained by polymerizing a single monomer or a mixture of two or more monomers. The polymerization can be carried out by some means such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization or the like. From the viewpoint of preventing contamination of clean adherends, the content of low molecular weight substances is preferably small. From this viewpoint, the number average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably about 200,000 to 3,000,000, and particularly preferably about 300,000 to 1,000,000.
另外，為了提高作為基礎聚合物之丙烯酸系聚合物等之數平均分子量，前述黏著劑中可以適當使用外部交聯劑。作為外部交聯方法之具體方法，可舉出：添加多異氰酸酯化合物、環氧化合物、氮丙啶化合物、三聚氰胺系交聯劑等所謂之交聯劑進行反應之方法。在使用外部 交聯劑之情況下，其使用量可以根據與應交聯之基礎聚合物之平衡、以及作為黏著劑之使用用途來適當確定。一般而言，相對於前述基礎聚合物100重量份，摻合5重量份左右以下，較佳為摻合0.1~5重量份。另外，根據需要，除前述成分之外，在黏著劑中還可以使用以往公知之各種增黏劑、抗老化劑等添加劑。 Further, in order to increase the number average molecular weight of the acrylic polymer or the like as the base polymer, an external crosslinking agent can be suitably used for the above-mentioned adhesive. Specific examples of the external crosslinking method include a method in which a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound or a melamine-based crosslinking agent is added to carry out a reaction. Using external In the case of a crosslinking agent, the amount thereof to be used can be appropriately determined depending on the balance with the base polymer to be crosslinked and the use as an adhesive. In general, it is blended in an amount of about 5 parts by weight or less, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the base polymer. Further, if necessary, in addition to the above-mentioned components, additives such as various conventionally known tackifiers and anti-aging agents may be used in the adhesive.
黏著劑層14可以利用輻射線硬化型黏著劑形成。輻射線硬化型黏著劑可以經由照射紫外線等輻射線使交聯度增大，從而容易地使其黏著力下降。 The adhesive layer 14 can be formed using a radiation hardening type adhesive. The radiation curable adhesive can increase the degree of crosslinking by irradiating radiation such as ultraviolet rays, thereby easily reducing the adhesion.
例如，經由與圖1所示之黏晶薄膜16之晶片黏貼部分16a相符地使射線硬化型黏著劑層14硬化，可以容易地形成黏著力顯著下降之前述部分14a。由於硬化而黏著力下降之前述部分14a上黏貼有黏晶薄膜16，因此黏著劑層14之前述部分14a與黏晶薄膜16之介面具有在拾取時容易剝離之性質。另一方面，未照射輻射線之部分具有充分之黏著力，形成前述部分14b。前述部分14b可以牢固地固定晶圓環。 For example, the portion 14a in which the adhesion is remarkably lowered can be easily formed by curing the radiation-curable adhesive layer 14 in conformity with the wafer adhering portion 16a of the adhesive film 16 shown in Fig. 1. Since the adhesive film 16 is adhered to the portion 14a where the adhesion is lowered due to hardening, the interface between the aforementioned portion 14a of the adhesive layer 14 and the die-bonding film 16 has a property of being easily peeled off at the time of picking up. On the other hand, the portion where the radiation is not irradiated has a sufficient adhesive force to form the aforementioned portion 14b. The aforementioned portion 14b can securely fix the wafer ring.
又，在以覆蓋整個切割片之方式在切割片上層合黏晶薄膜之情況下，可以在黏晶薄膜之外周部分固定晶圓環。 Further, in the case where the adhesive film is laminated on the dicing sheet so as to cover the entire dicing sheet, the wafer ring can be fixed to the outer peripheral portion of the dicing film.
輻射線硬化型黏著劑可以沒有特別限制地使用具有碳-碳雙鍵等輻射線硬化性官能基，且顯示出黏著性之黏著劑。作為輻射線硬化型黏著劑，可例示例如：在前述丙烯酸系黏著劑、橡膠系黏著劑等一般之壓敏性黏著劑中摻合有輻射線硬化性之單體成分或低聚物成分之添加 型之輻射線硬化型黏著劑。 As the radiation-curable adhesive, an adhesive having a radiation curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness can be used without particular limitation. As a radiation-curing type adhesive, for example, a radiation-hardening monomer component or an oligomer component is added to a general pressure-sensitive adhesive such as the acrylic pressure-sensitive adhesive or the rubber-based pressure-sensitive adhesive. Radiation hardening type adhesive.
作為所摻合之輻射線硬化性之單體成分，可以列舉例如：氨基甲酸酯低聚物、氨基甲酸酯(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等。另外，輻射線硬化性之低聚物成分可舉出氨基甲酸酯系、聚醚系、聚酯系、聚碳酸酯系、聚丁二烯系等各種之低聚物，其分子量在100~30000左右之範圍內是適當之。輻射線硬化性之單體成分或低聚物成分之摻合量，可以根據前述黏著劑層之種類來適當確定可使黏著劑層之黏著力下降之量。一般而言，相對於構成黏著劑之丙烯酸系聚合物等基礎聚合物100重量份，例如為5~500重量份、較佳為40~150重量份左右。 Examples of the radiation hardening monomer component to be blended include a urethane oligomer, a urethane (meth) acrylate, and a trimethylolpropane tri(meth) acrylate. Tetramethylol methane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(methyl) Acrylate, 1,4-butanediol di(meth)acrylate, and the like. Further, examples of the radiation curable oligomer component include various oligomers such as a urethane type, a polyether type, a polyester type, a polycarbonate type, and a polybutadiene type, and the molecular weight thereof is 100~. Within the range of around 30,000 is appropriate. The blending amount of the radiation curable monomer component or the oligomer component can be appropriately determined according to the kind of the above-mentioned adhesive layer to reduce the adhesive force of the adhesive layer. In general, it is, for example, 5 to 500 parts by weight, preferably 40 to 150 parts by weight, per 100 parts by weight of the base polymer such as the acrylic polymer constituting the pressure-sensitive adhesive.
另外，作為輻射線硬化型黏著劑，除前述說明過之添加型之輻射線硬化型黏著劑以外，還可舉出：使用在聚合物側鏈或者主鏈中或主鏈末端具有碳-碳雙鍵之聚合物作為基礎聚合物之內在型之輻射線硬化型黏著劑。就內在型之輻射線硬化型黏著劑而言，其不需要含有或者不大量含有作為低分子成分之低聚物成分等，因此低聚物成分等不會經時地在黏著劑中移動，從而可以形成穩定之層結構之黏著劑層，因此為佳。 Further, as the radiation curable adhesive, in addition to the radiation-curable adhesive of the above-described addition type, there may be mentioned that carbon-carbon double is used in the side chain or main chain of the polymer or at the end of the main chain. The polymer of the bond acts as an intrinsic type of radiation hardening adhesive for the base polymer. In the case of the intrinsic radiation-curable adhesive, it is not necessary to contain or contain a large amount of an oligomer component as a low molecular component, and therefore the oligomer component or the like does not move in the adhesive over time. It is preferred that an adhesive layer of a stable layer structure can be formed.
前述具有碳-碳雙鍵之基礎聚合物可以沒有特別限制地使用具有碳-碳雙鍵，且具有黏合性之基礎聚合物。作為此等之基礎聚合物，以丙烯酸系聚合物作為基本骨架之聚合物為佳。作為丙烯酸系聚合物之基本骨架，可舉出前述例示之丙烯酸系聚合物。 The base polymer having a carbon-carbon double bond as described above may be a base polymer having a carbon-carbon double bond and having adhesiveness without particular limitation. As such a base polymer, a polymer having an acrylic polymer as a basic skeleton is preferred. The basic skeleton of the acrylic polymer may, for example, be an acrylic polymer exemplified above.
於前述丙烯酸系聚合物中引入碳-碳雙鍵之方法沒有特別限制，可以採用各種方法，但在聚合物側鏈上引入碳-碳雙鍵在分子設計方面比較容易。例如可舉出下述方法：預先使具有官能基之單體與丙烯酸系聚合物共聚後，使具有可與該官能基反應之官能基、及碳-碳雙鍵之化合物，在保持碳-碳雙鍵之輻射線硬化性之狀態下進行縮合或加成反應。 The method of introducing the carbon-carbon double bond into the aforementioned acrylic polymer is not particularly limited, and various methods can be employed, but introduction of a carbon-carbon double bond on the side chain of the polymer is relatively easy in molecular design. For example, a method in which a monomer having a functional group and an acrylic polymer are copolymerized in advance, and a compound having a functional group reactive with the functional group and a carbon-carbon double bond is maintained while maintaining carbon-carbon The condensation or addition reaction is carried out in the state of radiation hardening of the double bond.
作為這些官能基之組合例，可以列舉：羧基與環氧基、羧基與氮丙啶基、羥基與異氰酸酯基等。此等官能基之組合中，從容易追蹤反應之觀點出發，羥基與異氰酸酯基之組合為佳。另外，只要是經由這些官能基之組合而生成前述具有碳-碳雙鍵之丙烯酸系聚合物之組合，則官能基可以在丙烯酸系聚合物與前述化合物中之任意一側，就前述組合而言為佳，丙烯酸系聚合物具有羥基、前述化合物具有異氰酸酯基之情形為佳。此時，作為具有碳-碳雙鍵之異氰酸酯化合物，可舉出例如甲基丙烯醯異氰酸酯、2-甲基丙烯醯氧乙基異氰酸酯、間異丙烯基-α,α-二甲基苄基異氰酸酯等。另外，作為丙烯酸系聚合物，可以使用將前述例示之含羥基單體或2-羥基乙基乙烯基醚、4- 羥基丁基乙烯基醚、二乙二醇單乙烯基醚之醚系化合物等共聚而得到之丙烯酸系聚合物。 Examples of the combination of these functional groups include a carboxyl group, an epoxy group, a carboxyl group and an aziridine group, a hydroxyl group and an isocyanate group. Among these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is preferred from the viewpoint of easily tracking the reaction. Further, as long as the combination of the above-mentioned functional groups is used to form a combination of the above-mentioned acrylic polymer having a carbon-carbon double bond, the functional group may be on either side of the acrylic polymer and the above compound, in terms of the aforementioned combination Preferably, the acrylic polymer has a hydroxyl group, and the compound has an isocyanate group. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryl oxime isocyanate, 2-methacryl oxirane ethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate. Wait. Further, as the acrylic polymer, the above-exemplified hydroxyl group-containing monomer or 2-hydroxyethyl vinyl ether, 4- An acrylic polymer obtained by copolymerization of an ether compound such as hydroxybutyl vinyl ether or diethylene glycol monovinyl ether.
前述內在型之輻射線硬化型黏著劑，可以單獨使用前述具有碳-碳雙鍵之基礎聚合物(特別是丙烯酸系聚合物)，也可以在不損害特性之程度下摻合前述輻射線硬化性之單體成分或低聚物成分。輻射線硬化性之低聚物成分等一般相對於基礎聚合物100重量份於30重量份之範圍內，0~10重量份之範圍為佳。 In the above-mentioned intrinsic radiation hardening type adhesive, the above-mentioned base polymer (especially an acrylic polymer) having a carbon-carbon double bond may be used alone, or the radiation hardenability may be blended to the extent that the properties are not impaired. a monomer component or an oligomer component. The radiation curable oligomer component or the like is generally in the range of 30 parts by weight based on 100 parts by weight of the base polymer, and preferably in the range of 0 to 10 parts by weight.
前述輻射線硬化型黏著劑中，在經由紫外線等而硬化之情況下含有光聚合引發劑。作為光聚合引發劑，可舉出例如：4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α’-二甲基苯乙酮、2-甲基-2-羥基苯丙酮、1-羥基環己基苯基酮等之α-酮醇系化合物；甲氧基苯乙酮、2,2’-二甲氧基-2-苯基苯乙酮、2,2’-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代丙烷-1-酮等之苯乙酮系化合物；苯偶姻***、苯偶姻異丙醚、茴香偶姻甲醚等之苯偶姻醚系化合物；苯偶醯二甲基縮酮等之縮酮系化合物；2-萘磺醯氯等之芳香族磺醯氯系化合物；1-苯酮-1,1-丙二酮-2-(鄰乙氧基羰基)肟等之光活性肟系化合物；二苯甲酮、苯甲醯基苯甲酸、3,3’-二甲基-4-甲氧基二苯甲酮等之二苯甲酮系化合物；噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2,4-二甲基噻噸酮、異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等之噻噸酮系化合物；樟腦醌；鹵代酮；醯基氧化膦；醯 基膦酸酯等。相對於構成黏著劑之丙烯酸系聚合物等之基礎聚合物100重量份，光聚合引發劑之摻合量例如為0.05重量份~20重量份左右。 The radiation curable adhesive contains a photopolymerization initiator when it is cured by ultraviolet rays or the like. The photopolymerization initiator may, for example, be 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)one or α-hydroxy-α,α'-dimethylacetophenone. An α-keto alcohol compound such as 2-methyl-2-hydroxypropiophenone or 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2′-dimethoxy-2-phenyl Phenylethyl acetophenone, 2,2'-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one a ketone compound; a benzoin ether compound such as benzoin ethyl ether, benzoin isopropyl ether or fennel methyl ether; a ketal compound such as benzoin dimethyl ketal; 2-naphthoquinone oxime Aromatic sulfonium chloride compound such as chlorine; photoactive lanthanide compound such as 1-benzophenone-1,1-propanedione-2-(o-ethoxycarbonyl)anthracene; benzophenone, benzamidine a benzophenone compound such as benzoic acid or 3,3'-dimethyl-4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Thiophenone ketone compound; camphor quinone; halogen Ketones; acyl phosphine oxide; XI Phosphonate and the like. The blending amount of the photopolymerization initiator is, for example, about 0.05 parts by weight to 20 parts by weight per 100 parts by weight of the base polymer of the acrylic polymer or the like constituting the pressure-sensitive adhesive.
另外，作為輻射線硬化型黏著劑，可舉出例如日本特開昭60-196956號公報中公開之橡膠系黏著劑或丙烯酸系黏著劑等，前述橡膠系黏著劑或丙烯酸系黏著劑等包含：具有兩個以上不飽和鍵之加聚性化合物、具有環氧基之烷氧基矽烷等之光聚合性化合物、與羰基化合物、有機硫化合物、過氧化物、胺、鎓鹽系化合物等之光聚合引發劑。 In addition, as the radiation-curable adhesive, for example, a rubber-based adhesive or an acrylic adhesive disclosed in JP-A-60-196956, the rubber-based adhesive or acrylic adhesive includes: Photopolymerizable compound having two or more unsaturated bonds, a photopolymerizable compound such as an alkoxysilane having an epoxy group, and a light compound such as a carbonyl compound, an organic sulfur compound, a peroxide, an amine or a phosphonium salt compound Polymerization initiator.
輻射線硬化型之黏著劑層14中，可以根據需要含有經由輻射線照射而著色之化合物。經由在黏著劑層14中含有經由輻射線照射而著色之化合物，可以僅使被輻射線照射後之部分著色。即，可以將圖1所示之與晶圓黏貼部分16a對應之部分14a著色。由此，可以經由目視直接判斷黏著劑層14是否被照射了輻射線，可以容易識別晶圓黏貼部分16a，工件之黏貼也容易。另外，在利用光感測器等檢測半導體晶片時，其檢測精度高，從而在半導體晶片之拾取時不產生誤操作。 In the radiation-curable adhesive layer 14, a compound colored by irradiation with radiation may be contained as needed. By including the compound colored by irradiation with radiation in the adhesive layer 14, only a portion irradiated with the radiation can be colored. That is, the portion 14a corresponding to the wafer sticking portion 16a shown in Fig. 1 can be colored. Thereby, it is possible to directly judge whether or not the adhesive layer 14 is irradiated with radiation by visual observation, and the wafer adhering portion 16a can be easily identified, and the adhesion of the workpiece is also easy. Further, when a semiconductor wafer is detected by a photo sensor or the like, the detection accuracy is high, so that no erroneous operation occurs at the time of picking up the semiconductor wafer.
經由照射輻射線而著色之化合物，為在照射輻射線前無色或淺色，但是經由照射輻射線而有色之化合物。作為前述化合物之較佳具體例具體例，可例如隱色染料(leuco dye)。作為隱色染料，可以使用慣用之三苯基甲烷系、熒烷系、吩噻嗪系、金胺系、螺吡喃系隱色染料為 佳。具體地可以列舉：3-[N-(對甲苯基胺基)]-7-苯胺基熒烷、3-[N-(對甲苯基)-N-甲基胺基]-7-苯胺基熒烷、3-[N-(對甲苯基)-N-乙基胺基]-7-苯胺基熒烷、3-二乙胺基-6-甲基-7-苯胺基熒烷、結晶紫內酯、4,4’,4”-三(二甲胺基)三苯基甲醇、4,4’,4”-三(二甲胺基)三苯基甲烷等。 A compound that is colored by irradiation with radiation is a compound that is colorless or light-colored before irradiation of radiation, but is colored by irradiation of radiation. As a specific example of a preferable specific example of the above compound, for example, a leuco dye can be used. As the leuco dye, a conventional triphenylmethane-based, fluoran-based, phenothiazine-based, gold-amine-based, spiropyran-based leuco dye can be used. good. Specifically, it can be mentioned that 3-[N-(p-tolylamino)]-7-anilinofluoran, 3-[N-(p-tolyl)-N-methylamino]-7-anilinylfluorene Alkane, 3-[N-(p-tolyl)-N-ethylamino]-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, crystal violet Ester, 4,4',4"-tris(dimethylamino)triphenylmethanol, 4,4',4"-tris(dimethylamino)triphenylmethane, and the like.
作為與此等隱色染料一起使用之顯色劑為佳，可以列舉一直以來使用之酚醛清漆樹脂之預聚物、芳香族羧酸衍生物、活性白土等之電子受體，另外，在要使色調變化時，可以將各種發色劑組合使用。 The coloring agent to be used together with these leuco dyes is preferably an electron acceptor such as a prepolymer of a novolak resin, an aromatic carboxylic acid derivative or an activated clay which has been conventionally used, and When the color tone changes, various coloring agents can be used in combination.
如此之經由照射輻射線而著色之化合物，可以先溶解於有機溶劑等中後再包含到輻射線硬化型接著劑中，另外，也可以以細粉末形式包含在該黏著劑中。該化合物之使用比例期望在黏著劑層14中為10重量%以下，0.01~10重量%為佳，較佳為0.5~5重量%。若該化合物之比例超過10重量%，則照射到黏著劑層14之輻射線被該化合物過度吸收，因此黏著劑層14之前述部分14a之硬化不充分，有時黏著力下降不充分。另一方面，為了充分地著色，使該化合物之比例為0.01重量%以上為佳。 The compound which is colored by irradiation with radiation may be dissolved in an organic solvent or the like and then incorporated into a radiation curable adhesive, or may be contained in the adhesive as a fine powder. The ratio of use of the compound is desirably 10% by weight or less in the adhesive layer 14, preferably 0.01 to 10% by weight, preferably 0.5 to 5% by weight. When the ratio of the compound exceeds 10% by weight, the radiation applied to the adhesive layer 14 is excessively absorbed by the compound. Therefore, the portion 14a of the adhesive layer 14 is insufficiently cured, and the adhesion may be insufficiently lowered. On the other hand, in order to sufficiently color, the ratio of the compound is preferably 0.01% by weight or more.
在由輻射線硬化型黏著劑形成黏著劑層14之情況下，可以以黏著劑層14中前述部分14a之黏著力<其他部分14b之黏著力之方式對黏著劑層14之一部分進行輻射線照射。 In the case where the adhesive layer 14 is formed of a radiation-curable adhesive, a part of the adhesive layer 14 may be irradiated with radiation of the adhesion of the aforementioned portion 14a in the adhesive layer 14 to the other portion 14b. .
作為在黏著劑層14形成前述部分14a之方法，可舉出：在基材12上形成輻射線硬化型黏著劑層14 後，對前述部分14a局部地照射輻射線使其硬化之方法。局部之輻射線照射可以經由形成有與黏晶薄膜16晶圓黏貼部分16a以外之部分對應之圖案之光掩模來進行。另外，可舉出點狀照射紫外線進行硬化之方法等。輻射線硬化型之黏著劑層14之形成可以經由將設置在隔片上之輻射線硬化型之黏著劑層轉印到基材12上來進行。局部之輻射線硬化也可以對設置在隔片上之輻射線硬化型之黏著劑層14進行。 As a method of forming the aforementioned portion 14a in the adhesive layer 14, a radiation-curable adhesive layer 14 is formed on the substrate 12. Thereafter, the portion 14a is partially irradiated with radiation to harden it. The local radiation irradiation can be performed through a photomask formed with a pattern corresponding to a portion other than the wafer bonding portion 16a of the die-bonding film 16. Further, a method of curing by spotting with ultraviolet rays or the like can be mentioned. The formation of the radiation-curable adhesive layer 14 can be carried out by transferring the radiation-curable adhesive layer provided on the separator to the substrate 12. Localized radiation hardening can also be performed on the radiation-curable adhesive layer 14 disposed on the spacer.
另外，經由輻射線硬化型黏著劑形成黏著劑層14之情況下，可以使用對基材12之至少單面之、與晶圓黏貼部分16a對應之部分以外之部分之全部或局部進行遮光之基材，並於該基材上形成輻射線硬化型黏著劑層14後進行輻射線照射，使與晶圓黏貼部分16a對應之部分硬化，從而形成黏著力下降之前述部分14a。作為遮光材料，可以經由印刷或蒸鍍等在支撐薄膜上製作可成為光掩模之材料。經由所述製造方法，可以有效地製造附有切割片之黏晶薄膜10。 Further, when the adhesive layer 14 is formed by the radiation-curable adhesive, it is possible to use a light-shielding base for all or part of a portion other than the portion corresponding to the wafer adhering portion 16a on at least one side of the substrate 12. After the radiation-curable adhesive layer 14 is formed on the substrate, radiation is irradiated to partially cure the portion corresponding to the wafer adhering portion 16a, thereby forming the portion 14a where the adhesive force is lowered. As the light-shielding material, a material that can be used as a photomask can be formed on the support film by printing, vapor deposition, or the like. Through the manufacturing method, the die-bonding film 10 with the dicing sheet attached can be efficiently manufactured.
又，進行輻射線照射時因氧產生硬化障礙之情況下，利用某種方法從輻射線硬化型之黏著劑層14之表面隔絕氧(空氣)。作為隔絕氧的方法，可舉出例如：用隔片將黏著劑層14之表面覆蓋之方法或者於氮氣氛圍中進行紫外線等輻射線之照射之方法等。 Further, in the case where radiation hardening is caused by irradiation of radiation, oxygen (air) is isolated from the surface of the radiation-curable adhesive layer 14 by some method. Examples of the method of isolating oxygen include a method of covering the surface of the adhesive layer 14 with a separator or a method of irradiating a radiation such as ultraviolet rays in a nitrogen atmosphere.
黏著劑層14之厚度沒有特別限定，但從兼具防止晶片切割面之缺損或黏晶薄膜16之固定保持等方面 考慮，為1μm~50μm左右為佳。較佳為2μm~30μm、更佳為5μm~25μm。 The thickness of the adhesive layer 14 is not particularly limited, but it has both the prevention of the defect of the cut surface of the wafer or the fixing of the die-bonding film 16 and the like. It is preferable that it is about 1 μm to 50 μm. It is preferably 2 μm to 30 μm, more preferably 5 μm to 25 μm.
附有切割片之黏晶薄膜10之黏晶薄膜16由隔片保護(未圖示)為佳。隔片具有在供給實際應用之前作為保護黏晶薄膜16之保護材料之功能。另外，隔片還可以作為向黏著劑層14轉印黏晶薄膜16時之支撐基材使用。隔片在向附有切割片之黏晶薄膜10之黏晶薄膜16上黏貼工件(半導體晶圓)時剝離。作為隔片，可以使用聚對苯二甲酸乙二醇酯(PET)、聚乙烯、聚丙烯，也可以使用由含氟剝離劑、長鏈烷基丙烯酸酯系剝離劑等剝離劑進行了表面塗敷之塑膠膜或紙等。 The adhesive film 16 with the dicing film 10 is preferably protected by a spacer (not shown). The separator has a function as a protective material for protecting the die-bonding film 16 before being supplied to the actual application. Further, the separator can also be used as a support substrate when the adhesive film 16 is transferred to the adhesive layer 14. The separator is peeled off when the workpiece (semiconductor wafer) is adhered to the die-bonded film 16 to which the dicing film 10 is attached. As the separator, polyethylene terephthalate (PET), polyethylene, or polypropylene may be used, or a surface coating agent may be used using a release agent such as a fluorine-containing release agent or a long-chain alkyl acrylate release agent. Apply plastic film or paper.
關於本實施方式之附有切割片之黏晶薄膜10例如如下所述地進行製作。 The die-bonding film 10 with a dicing sheet according to the present embodiment is produced, for example, as follows.
首先，基材12可以經由以往公知之成膜方法成膜。作為該成膜方法，可以例示例如：壓延成膜法、有機溶劑中之澆鑄法、密閉體系中之吹塑擠出法、T形模頭擠出法、共擠出法、乾式層壓法等。 First, the substrate 12 can be formed into a film by a conventionally known film formation method. Examples of the film formation method include a calender film formation method, a casting method in an organic solvent, a blow extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, a dry lamination method, and the like. .
然後，經由在基材12上塗佈黏著劑組合物溶液形成塗膜後，將該塗膜在預定條件下進行乾燥(根據需要進行加熱交聯)，形成黏著劑層14。作為塗佈方法，沒有特別限制，可舉出例如：輥塗佈、絲網塗佈、凹版塗佈等。另外，作為乾燥條件，可以為例如在乾燥溫度80℃~150℃、乾燥時間0.5分鐘~5分鐘之範圍內進行。另外，也可以於隔片上塗佈黏著劑組合物形成塗佈膜後，在 前述乾燥條件下使塗佈膜乾燥而形成黏著劑層14。之後，將黏著劑層14與隔片一起黏貼到基材12上。由此，製作切割片11。 Then, after a coating film is formed by applying an adhesive composition solution onto the substrate 12, the coating film is dried under predetermined conditions (heat-crosslinking if necessary) to form an adhesive layer 14. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. Further, the drying conditions may be, for example, a drying temperature of 80 ° C to 150 ° C and a drying time of 0.5 minutes to 5 minutes. Alternatively, after the adhesive composition is applied to the separator to form a coating film, The coating film is dried under the aforementioned drying conditions to form the adhesive layer 14. Thereafter, the adhesive layer 14 is adhered to the substrate 12 together with the separator. Thereby, the cut piece 11 is produced.
黏晶薄膜16例如如下所述製作。 The die-shaped film 16 is produced, for example, as follows.
首先，製作作為黏晶薄膜16之形成材料之接著劑組合物溶液。該接著劑組合物溶液如前所述摻合有前述樹脂或其他根據需要之各種添加劑等。 First, a solution of an adhesive composition as a material for forming the adhesive film 16 is produced. The adhesive composition solution is blended with the aforementioned resin or other various additives as needed, as described above.
接者，將接著劑組合物溶液塗佈到基材隔片上達到預定之厚度而形成塗佈膜，然後在預定條件下使該塗佈膜乾燥，形成黏晶薄膜16。作為塗佈方法，沒有特別限制，可舉出例如：輥塗佈、絲網塗佈、凹版塗佈等。另外，作為乾燥條件，可以為例如於乾燥溫度70℃~160℃、乾燥時間1分鐘~5分鐘之範圍內進行。另外，也可以於隔片上塗佈接著劑組合物溶液形成塗佈膜後，於前述乾燥條件下使塗佈膜乾燥而形成黏晶薄膜16。之後，將接著劑層與隔片一起黏貼到基材隔片上。 Then, the adhesive composition solution is applied onto the substrate separator to a predetermined thickness to form a coating film, and then the coating film is dried under predetermined conditions to form a die-shaped film 16. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. Further, the drying conditions may be, for example, a drying temperature of 70 ° C to 160 ° C and a drying time of 1 minute to 5 minutes. Alternatively, the coating film may be formed by applying an adhesive composition solution to the separator, and then drying the coating film under the drying conditions to form the die-bonding film 16. Thereafter, the adhesive layer is adhered to the substrate separator together with the separator.
接著，從切割片11和黏晶薄膜16上分別剝離隔片，以接著劑層14與黏晶薄膜16成為貼合面之方式將兩者貼合。貼合可以經由例如壓接來進行。此時，層合溫度沒有特別限制，例如30℃~50℃為佳，較佳為35℃~45℃。另外，線壓沒有特別限制，例如0.1kgf/cm~20kgf/cm為佳，較佳為1kgf/cm~10kgf/cm。由此，可得到附有切割片之黏晶薄膜10。 Next, the separator is peeled off from the dicing sheet 11 and the die-bonding film 16, and the adhesive layer 14 and the die-bonding film 16 are bonded to each other so that the adhesive layer 14 and the die-bonding film 16 become a bonding surface. The bonding can be performed via, for example, crimping. At this time, the lamination temperature is not particularly limited, and is preferably, for example, 30 ° C to 50 ° C, preferably 35 ° C to 45 ° C. Further, the linear pressure is not particularly limited, and is preferably, for example, 0.1 kgf/cm to 20 kgf/cm, preferably 1 kgf/cm to 10 kgf/cm. Thereby, the adhesive film 10 with the dicing sheet attached can be obtained.
接者，對半導體裝置之製造方法進行說明。 Next, a method of manufacturing a semiconductor device will be described.
以下，對使用了附有切割片之黏晶薄膜10之半導體裝置之製造方法進行說明。 Hereinafter, a method of manufacturing a semiconductor device using the die-bonded film 10 with a dicing sheet will be described.
關於本實施方式之半導體裝置之製造方法包括：準備步驟，準備前述之附有切割片之黏晶薄膜、與貼合步驟，將前述附有切割片之黏晶薄膜之黏晶薄膜與半導體晶片之背面貼合、與切割步驟，將前述半導體晶片與前述黏晶薄膜一起切割，形成晶片狀之半導體晶片、與拾取步驟，將前述半導體晶片與前述黏晶薄膜一起從前述附有切割片之黏晶薄膜拾取、與黏晶步驟，經由前述黏晶薄膜於被黏物上黏晶前述半導體晶片、與密封步驟，於前述黏晶步驟之後，利用密封樹脂將前述半導體晶片密封。 The manufacturing method of the semiconductor device of the present embodiment includes a preparation step of preparing the above-mentioned dicing film with a dicing sheet, and a bonding step of laminating the viscous film with the dicing sheet and the semiconductor wafer. a back surface bonding and cutting step, cutting the semiconductor wafer together with the die-bonding film to form a wafer-shaped semiconductor wafer, and a picking step, and the semiconductor wafer and the die-bonding film together with the die-bonded die The film picking and bonding step, the semiconductor wafer is adhered to the adherend via the die film, and the sealing step is performed, and after the bonding step, the semiconductor wafer is sealed with a sealing resin.
關於本實施方式之半導體裝置之製造方法中，首先，準備附有切割片之黏晶薄膜10(準備步驟)。對於附有切割片之黏晶薄膜10而言，將任意設置於黏晶薄膜16上之隔片適當剝離後，如下所述地使用。以下，參照圖1及圖2，以使用附有切割片之黏晶薄膜10之情況為例進行說明。 In the method of manufacturing a semiconductor device of the present embodiment, first, a die-bonding film 10 having a dicing sheet is prepared (preparation step). For the die-bonded film 10 with the dicing sheet, the separator arbitrarily provided on the die-bonding film 16 is appropriately peeled off, and then used as described below. Hereinafter, a case where the die-bonded film 10 with a dicing sheet is used will be described as an example with reference to FIGS. 1 and 2.
首先，將半導體晶圓4壓接於附有切割片之 黏晶薄膜10中之黏晶薄膜16之半導體晶圓黏貼部分16a上，使其接著保持而固定(黏貼步驟)。本步驟於用壓接輥等之擠壓手段擠壓之同時進行。安裝時之黏貼溫度沒有特別限制，例如於40~90℃之範圍內為佳。本步驟於實質上不伴隨黏晶薄膜16之反應(例如，交聯結構之形成)之範圍內設定條件為佳。 First, the semiconductor wafer 4 is crimped to the attached dicing sheet. The semiconductor wafer adhering portion 16a of the adhesive film 16 in the adhesive film 10 is then held and fixed (adhesion step). This step is carried out simultaneously with extrusion by a pressing means such as a crimping roller. The bonding temperature at the time of mounting is not particularly limited, and is preferably in the range of 40 to 90 ° C, for example. This step is preferably set within a range that does not substantially accompany the reaction of the die-bonding film 16 (for example, formation of a crosslinked structure).
接著，進行半導體晶圓4之切割(切割步驟)。由此，將半導體晶圓4切割為預定之尺寸而單片化，製造半導體晶片5。切割之方法沒有特別限制，例如從半導體晶圓4之電路面一側按照常規方法來進行。另外，本步驟中，例如可以採用切入至附有切割片之黏晶薄膜10處之稱為全切之切割方式等。本步驟中使用之切割裝置沒有特別限制，可以使用以往公知之切割裝置。另外，由於半導體晶圓4經由附有切割片之黏晶薄膜10接著固定，因此可以抑制晶片缺損或晶片飛散，同時也可以抑制半導體晶圓4之破損。 Next, the dicing of the semiconductor wafer 4 (cutting step) is performed. Thereby, the semiconductor wafer 4 is diced into a predetermined size and singulated to fabricate the semiconductor wafer 5. The method of cutting is not particularly limited, and is performed, for example, from the side of the circuit surface of the semiconductor wafer 4 in accordance with a conventional method. Further, in this step, for example, a cutting method called a full cut which is cut into the die-bonded film 10 with the dicing sheet may be employed. The cutting device used in this step is not particularly limited, and a conventionally known cutting device can be used. Further, since the semiconductor wafer 4 is then fixed via the die-bonding film 10 with the dicing sheet, wafer defects or wafer scattering can be suppressed, and damage of the semiconductor wafer 4 can be suppressed.
接著為了將接著固定在附有切割片之黏晶薄膜10之半導體晶片5剝離，進行半導體晶片5之拾取(拾取步驟)。拾取方法沒有特別限制，可以使用以往公知之各種方法。例如，可舉出用針從附有切割片之黏晶薄膜10一側將各個半導體晶片5上推，經由拾取裝置拾取被上推之半導體晶片5之方法等。 Next, in order to peel off the semiconductor wafer 5 which is then fixed to the die-bonded film 10 with the dicing sheet, the pickup of the semiconductor wafer 5 is carried out (pickup step). The picking method is not particularly limited, and various methods known in the art can be used. For example, a method in which each semiconductor wafer 5 is pushed up from the side of the die-bonded film 10 with the dicing sheet by a needle, and the semiconductor wafer 5 pushed up by the pick-up device is picked up.
作為拾取條件，從防止崩裂之觀點出發，使針上推速度為5~100mm/秒為佳，較佳5~10mm/秒。 As the pick-up condition, from the viewpoint of preventing cracking, the needle push-up speed is preferably 5 to 100 mm/sec, preferably 5 to 10 mm/sec.
在此，黏著劑層14為輻射線硬化型時，拾取在對該黏著劑層14照射輻射線後進行。由此，黏著劑層14對黏晶薄膜16之黏著力降低，半導體晶片5之剝離變得容易。結果，可以在不損傷半導體晶片5之情況下進行拾取。輻射線照射時之照射強度、照射時間等條件沒有特別限制，可以根據需要適當設定。另外，作為用於輻射線照射之光源，可以使用公知之光源。又，預先對黏著劑層照射輻射線使其硬化，並將該硬化後之黏著劑層與黏晶薄膜貼合之情況下，不需要此處之輻射線照射。 Here, when the adhesive layer 14 is of a radiation curing type, the pickup is performed after irradiating the adhesive layer 14 with radiation. Thereby, the adhesive force of the adhesive layer 14 to the die-bonding film 16 is lowered, and the peeling of the semiconductor wafer 5 becomes easy. As a result, pickup can be performed without damaging the semiconductor wafer 5. The conditions such as the irradiation intensity and the irradiation time at the time of radiation irradiation are not particularly limited, and can be appropriately set as needed. Further, as a light source for radiation irradiation, a known light source can be used. Further, in the case where the adhesive layer is irradiated with radiation to be hardened in advance, and the cured adhesive layer is bonded to the adhesive film, the radiation irradiation here is not required.
接著，拾取之半導體晶片5透過黏晶薄膜16接著固定到被黏物6上(黏晶步驟)。作為被黏物6，可舉出引線框、TAB膜、基板或另外製作之半導體晶片等。被黏物6例如可以為容易變形之變形型被黏物，也可以為不易變形之非變形型被黏物(半導體晶圓等)。本步驟於實質上不伴隨黏晶薄膜16之反應(例如，交聯結構之形成)之範圍內設定條件為佳。 Next, the picked semiconductor wafer 5 is then fixed to the adherend 6 through the die-bonding film 16 (bonding step). Examples of the adherend 6 include a lead frame, a TAB film, a substrate, and a separately fabricated semiconductor wafer. The adherend 6 may be, for example, a deformed adherend that is easily deformed, or a non-deformable adherend that is not easily deformed (a semiconductor wafer or the like). This step is preferably set within a range that does not substantially accompany the reaction of the die-bonding film 16 (for example, formation of a crosslinked structure).
作為前述基板，可以使用以往公知之基板。另外，作為前述引線框，可以使用Cu引線框、42合金引線框等之金屬引線框、或者由玻璃環氧、BT(雙馬來醯亞胺-三嗪)、聚醯亞胺等製成之有機基板。但是，本發明不限於這些，也包括魚安裝半導體晶片並與半導體晶片電連接後可以使用之電路板。 As the substrate, a conventionally known substrate can be used. Further, as the lead frame, a metal lead frame such as a Cu lead frame or a 42 alloy lead frame or a glass epoxy, BT (bismaleimide-triazine), polyimine or the like can be used. Organic substrate. However, the present invention is not limited to these, and includes a circuit board which can be used after the fish is mounted with a semiconductor wafer and electrically connected to the semiconductor wafer.
然後，如圖2所示，根據需要用引線接合7將被黏物6之端子部(內部引線)之前端與半導體晶片5 上之電極墊(die pad)(未圖示)電連接(引線接合步驟)。作為前述引線接合7，可以使用例如金線、鋁線或銅線等。進行引線接合時之溫度為80℃~250℃，80℃~220℃之範圍為佳。另外，其加熱時間為幾秒~幾分鐘。接線於加熱至前述溫度範圍內之狀態下，經由組合使用超音波之振動能與加壓之壓接能來進行。本步驟於實質上不伴隨黏晶薄膜16之反應(例如，交聯結構之形成)之範圍內設定條件為佳。 Then, as shown in FIG. 2, the terminal portion (internal lead) of the adherend 6 is bonded to the semiconductor wafer 5 by wire bonding 7 as needed. The upper electrode pad (not shown) is electrically connected (wire bonding step). As the wire bonding 7 described above, for example, a gold wire, an aluminum wire, a copper wire, or the like can be used. The temperature at the time of wire bonding is 80 ° C to 250 ° C, and the range of 80 ° C to 220 ° C is preferable. In addition, the heating time is from a few seconds to a few minutes. The wiring is heated to a temperature within the aforementioned temperature range, and the vibration energy of the ultrasonic wave and the pressure-bonding energy of the pressurization are used in combination. This step is preferably set within a range that does not substantially accompany the reaction of the die-bonding film 16 (for example, formation of a crosslinked structure).
接著，於設置多段半導體晶片之情況下，可以於半導體晶片5上進一步黏晶附有黏晶薄膜之其他半導體晶片(未圖示)。此時，作為黏晶薄膜，可使用其他黏晶薄膜，但使用黏晶薄膜16為佳。作為黏晶條件，可以與半導體晶片5之黏晶條件同樣。之後，根據需要，用引線接合將被黏物6之端子部之前端與前述其他半導體晶片上之電極墊電連接(引線接合步驟)。作為引線接合條件，可以與半導體晶片5之引線接合條件同樣。 Next, in the case where a plurality of semiconductor wafers are provided, another semiconductor wafer (not shown) having a die-bonding film attached thereto may be further adhered to the semiconductor wafer 5. At this time, as the die-bonding film, other die-bonding films can be used, but the die-bonding film 16 is preferably used. The conditions of the die bonding can be the same as those of the semiconductor wafer 5. Thereafter, the front end of the terminal portion of the adherend 6 is electrically connected to the electrode pad on the other semiconductor wafer by wire bonding as needed (wire bonding step). The wire bonding conditions can be the same as the wire bonding conditions of the semiconductor wafer 5.
接著，如圖2所示，利用密封樹脂8將半導體晶片5密封(密封步驟)。本步驟是為了保護搭載於被黏物6上之半導體晶片5或引線接合7等而進行。本步驟經由用模具將密封用樹脂成形來進行。作為密封樹脂8，例如使用環氧樹脂。於設置多段半導體晶片之情況下，利用密封樹脂8將半導體晶片5及前述其他半導體晶片密封(未圖示)。樹脂密封時之加熱溫度一般於175℃下進行60秒~90秒，但是，本發明不限於此，例如也可以於165 ℃~185℃下進行幾分鐘硬化。 Next, as shown in FIG. 2, the semiconductor wafer 5 is sealed by the sealing resin 8 (sealing step). This step is performed to protect the semiconductor wafer 5 or the wire bonding 7 or the like mounted on the adherend 6. This step is carried out by molding a resin for sealing with a mold. As the sealing resin 8, for example, an epoxy resin is used. When a plurality of semiconductor wafers are provided, the semiconductor wafer 5 and the other semiconductor wafers are sealed by a sealing resin 8 (not shown). The heating temperature at the time of resin sealing is generally performed at 175 ° C for 60 seconds to 90 seconds, but the present invention is not limited thereto, and for example, may also be 165 Hardening for a few minutes at °C~185°C.
關於黏晶薄膜16，加熱處理前於150℃下之儲存彈性模量E’1為10MPa以下，比較具有柔軟性。因此，即使於黏晶步驟中產生空隙，也可以利用密封步驟中之壓力，使該空隙在不發生膨脹之情況下分散於樹脂中，從而使其在視覺上消失。結果，可降低空隙之影響。 Regarding the die-bonding film 16, the storage elastic modulus E'1 at 150 ° C before the heat treatment is 10 MPa or less, and is relatively flexible. Therefore, even if a void is generated in the die-bonding step, the pressure in the sealing step can be utilized to disperse the void in the resin without being expanded, thereby causing it to visually disappear. As a result, the influence of the voids can be reduced.
另外，關於黏晶薄膜16，前述E’1與於150℃下加熱1小時後於150℃下之儲存彈性模量E’2之差(E’2-E’1)為5MPa以下，從而具有不易因密封步驟前之熱歷程(例如，多次黏晶步驟中之熱)而變硬之性質。因此，即使在經歷晶片之多段化等所致之長之熱歷程後，也可經由密封步驟中之壓力使空隙在視覺上消失。结果，可降低空隙降低空隙之影響。 Further, regarding the die-bonding film 16, the difference (E'2-E'1) between the above-mentioned E'1 and the storage elastic modulus E'2 at 150 ° C after heating at 150 ° C for 1 hour is 5 MPa or less, thereby having It is not easy to be hardened due to the thermal history before the sealing step (for example, the heat in the multiple bonding step). Therefore, even after a long thermal history due to the multi-stage of the wafer or the like, the void can be visually disappeared via the pressure in the sealing step. As a result, the effect of voids to reduce voids can be reduced.
又，本密封步驟中，也可以採用在作為密封樹脂8之片狀之密封用片中埋入半導體晶片5之方法(例如，參照日本特開2013-7028號公報)。 In the sealing step, a method of embedding the semiconductor wafer 5 in the sheet-like sealing sheet as the sealing resin 8 may be employed (for example, refer to Japanese Laid-Open Patent Publication No. 2013-7028).
接者，對黏晶薄膜16進行加熱來形成交聯結構，將半導體晶片5接著固定於被黏物6，提高耐熱強度(交聯形成步驟)。可以於80~200℃、100~175℃為佳、較佳為100~140℃之加熱溫度下進行。另外，可以以0.1~24小時、0.1~3小時為佳、較佳為0.2~1小時之加熱時間進行。另外，交聯形成可以於加壓條件下進行。作為加壓條件，1~20kg/cm2之範圍為佳，較佳為3~15kg/cm2之範圍。加壓下之交聯形成例如可以在填充有不活潑氣體 之腔室內進行。 Then, the die-bonding film 16 is heated to form a crosslinked structure, and the semiconductor wafer 5 is subsequently fixed to the adherend 6 to improve heat resistance (crosslinking forming step). It can be carried out at a heating temperature of preferably from 80 to 200 ° C and from 100 to 175 ° C, preferably from 100 to 140 ° C. Further, it may be carried out in a heating time of 0.1 to 24 hours, 0.1 to 3 hours, preferably 0.2 to 1 hour. Further, the crosslinking formation can be carried out under pressurized conditions. The pressing condition is preferably in the range of 1 to 20 kg/cm 2 , and more preferably in the range of 3 to 15 kg/cm 2 . Crosslinking under pressure can be carried out, for example, in a chamber filled with an inert gas.
關於黏晶薄膜16，以如下方式進行設計：不易經由交聯形成步驟之前之步驟中之熱(例如，黏晶步驟中之熱等)引起交聯形成之反應，且經由交聯形成步驟中之熱來形成交聯為佳。另外，以可發揮出該功能之方式來設定黏晶步驟中之加熱條件為佳或交聯形成步驟中之加熱條件。 The die-bonding film 16 is designed in such a manner that it is difficult to cause a reaction of crosslinking formation by heat in the step before the crosslinking forming step (for example, heat in the die bonding step, etc.), and is formed in the crosslinking forming step. It is better to form crosslinks by heat. Further, it is preferable to set the heating conditions in the die bonding step or the heating conditions in the crosslinking forming step in such a manner that the function can be exhibited.
接者，根據需要進一步進行加熱，將在前述密封步驟中硬化不充分之密封樹脂8進行完全硬化(後硬化步驟)。本步驟中之加熱溫度根據密封樹脂之種類之不同而不同，例如於165℃~185℃之範圍內，加熱時間為0.5小時~8小時左右。 Further, if necessary, further heating is performed to completely cure the sealing resin 8 which is insufficiently hardened in the sealing step (post-hardening step). The heating temperature in this step varies depending on the type of the sealing resin, for example, in the range of 165 ° C to 185 ° C, and the heating time is about 0.5 to 8 hours.
以下，例示性地詳細說明本發明較佳之實施例。但是，該實施例中記載之材料或摻合量等只要沒有特別限定性之記載，就不將本發明之要旨僅限定在該範圍內。又，以下中，份係指重量份。 Hereinafter, preferred embodiments of the present invention will be exemplarily described in detail. However, the materials, blending amounts, and the like described in the examples are not intended to limit the scope of the invention, unless otherwise specified. In the following, the parts are parts by weight.
於甲乙酮中溶解下述(a)~(b)，得到濃度23重量%之接著劑組合物溶液。 The following (a) to (b) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 23% by weight.
將該接著劑組合物溶液塗佈到矽酮脫模處理後之厚度為38μm之聚對苯二甲酸乙二醇酯膜形成之脫模處理膜(剝離襯墊)上後，於130℃下乾燥2分鐘。由此，製作厚度20μm之黏晶薄膜A。 The adhesive composition solution was applied onto a release-treated film (release liner) formed of a polyethylene terephthalate film having a thickness of 38 μm after the release treatment of the anthrone, and then dried at 130 ° C. 2 minutes. Thus, a microcrystalline film A having a thickness of 20 μm was produced.
在甲乙酮中溶解下述(a)~(c)，得到濃度23重量%之接著劑組合物溶液。 The following (a) to (c) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 23% by weight.
將該接著劑組合物溶液塗佈到矽酮脫模處理後之厚度為38μm之聚對苯二甲酸乙二醇酯膜形成之脫模處理膜(剝離襯墊)上後，於130℃下乾燥2分鐘。由此，製作厚度20μm之黏晶薄膜B。 The adhesive composition solution was applied onto a release-treated film (release liner) formed of a polyethylene terephthalate film having a thickness of 38 μm after the release treatment of the anthrone, and then dried at 130 ° C. 2 minutes. Thus, a microcrystalline film B having a thickness of 20 μm was produced.
於甲乙酮中溶解下述(a)~(b)，得到濃度23重量%之接著劑組合物溶液。 The following (a) to (b) were dissolved in methyl ethyl ketone to obtain a solution of an adhesive composition having a concentration of 23% by weight.
將該接著劑組合物溶液塗佈到矽酮脫模處理後之厚度為38μm之聚對苯二甲酸乙二醇酯膜形成之脫模處理膜(剝離襯墊)上後，於130℃下乾燥2分鐘。由 此，製作厚度20μm之黏晶薄膜C。 The adhesive composition solution was applied onto a release-treated film (release liner) formed of a polyethylene terephthalate film having a thickness of 38 μm after the release treatment of the anthrone, and then dried at 130 ° C. 2 minutes. by Thus, a microcrystalline film C having a thickness of 20 μm was produced.
於甲乙酮中溶解下述(a)~(e)，濃度23重量%之接著劑組合物溶液。 The following adhesive composition solution of (a) to (e) at a concentration of 23% by weight was dissolved in methyl ethyl ketone.
將該接著劑組合物溶液塗佈到矽酮脫模處理後之厚度為38μm之聚對苯二甲酸乙二醇酯膜形成之脫模 處理膜(剝離襯墊)上後，於130℃下乾燥2分鐘。由此，製作厚度20μm之黏晶薄膜D。 The adhesive composition solution is applied to a release film formed by a polyethylene terephthalate film having a thickness of 38 μm after the release treatment of the anthrone. After treating the film (release liner), it was dried at 130 ° C for 2 minutes. Thus, a microcrystalline film D having a thickness of 20 μm was produced.
於甲乙酮中溶解下述(a)~(e)，濃度23重量%之接著劑組合物溶液。 The following adhesive composition solution of (a) to (e) at a concentration of 23% by weight was dissolved in methyl ethyl ketone.
將該接著劑組合物溶液塗佈到矽酮脫模處理後之厚度為38μm之聚對苯二甲酸乙二醇酯膜形成之脫模處理膜(剝離襯墊)上後，在130℃下乾燥2分鐘。由此，製作厚度20μm之黏晶薄膜E。 The adhesive composition solution was applied onto a release-treated film (release liner) formed of a polyethylene terephthalate film having a thickness of 38 μm after the release treatment of the anthrone, and then dried at 130 ° C. 2 minutes. Thus, a microcrystalline film E having a thickness of 20 μm was produced.
對於實施例、比較例之黏晶薄膜，分別層合至厚度200μm，得到寬度10mm、長度40mm之測定樣品。然後，使用動態黏彈性測定裝置(RSA(III)，Rheometrics科技公司製)，於卡盤間距22.5mm、頻率10Hz、升溫速度10℃/分鐘之條件下測定-30~260℃下之拉伸儲存彈性模量及損失彈性模量。此時，150℃中之儲存彈性模量及150℃中之損失彈性模量如表1所示。另外，進行該測定時之損耗角正切tanδ1之峰值也如表1所示。 The adhesive films of the examples and the comparative examples were laminated to a thickness of 200 μm to obtain a measurement sample having a width of 10 mm and a length of 40 mm. Then, using a dynamic viscoelasticity measuring apparatus (RSA (III), manufactured by Rheometrics, Inc.), the tensile storage at -30 to 260 ° C was measured under the conditions of a chuck pitch of 22.5 mm, a frequency of 10 Hz, and a temperature rising rate of 10 ° C /min. Modulus of elasticity and loss modulus of elasticity. At this time, the storage elastic modulus at 150 ° C and the loss elastic modulus at 150 ° C are shown in Table 1. In addition, the peak value of the loss tangent tan δ1 at the time of this measurement is also shown in Table 1.
將關於實施例及比較例之黏晶薄膜於150℃下加熱1小時。然後，對於實施例、比較例之黏晶薄膜，分別層合至厚度200μm，得到寬度10mm、長度40mm之測定樣品。然後，使用動態黏彈性測定裝置(RSA(III)， Rheometrics科技公司製)，於卡盤間距22.5mm、頻率10Hz、升溫速度10℃/分鐘之條件下測定-30~260℃下之拉伸儲存彈性模量及損失彈性模量。此時，150℃下之儲存彈性模量及150℃下之損失彈性模量如表1所示。另外，進行該測定時之損耗角正切tanδ2之峰值也如表1所示。 The die-bonded films of the examples and the comparative examples were heated at 150 ° C for 1 hour. Then, the adhesive films of the examples and the comparative examples were laminated to a thickness of 200 μm to obtain a measurement sample having a width of 10 mm and a length of 40 mm. Then, using a dynamic viscoelasticity measuring device (RSA (III), Rheometrics Technology Co., Ltd.) The tensile storage elastic modulus and the loss elastic modulus at -30 to 260 ° C were measured under the conditions of a chuck pitch of 22.5 mm, a frequency of 10 Hz, and a temperature increase rate of 10 ° C/min. At this time, the storage elastic modulus at 150 ° C and the loss elastic modulus at 150 ° C are shown in Table 1. In addition, the peak value of the loss tangent tan δ2 at the time of this measurement is also shown in Table 1.
從上述測定之結果求出差(E’2-E’1)、比(E’1/E’2)、差(E”2-E”1)、比(E”1/E”2)、差(tanδ2-tanδ1)。結果如表1所示。 From the results of the above measurement, the difference (E'2-E'1), the ratio (E'1/E'2), the difference (E"2-E"1), the ratio (E"1/E"2), Poor (tan δ 2-tan δ 1). The results are shown in Table 1.
對於實施例、比較例之黏晶薄膜，分別層合至厚度200μm，得到寬度10mm、初始長度40mm之測定樣品。接著，使用拉伸試驗機(島津製作公司製)於拉伸速度300mm/分鐘、卡盤間距10mm之條件下測定25℃下之拉伸斷裂伸長率。結果如表1所示。 The adhesive films of the examples and the comparative examples were laminated to a thickness of 200 μm to obtain a measurement sample having a width of 10 mm and an initial length of 40 mm. Next, the tensile elongation at break at 25 ° C was measured under the conditions of a tensile speed of 300 mm/min and a chuck pitch of 10 mm using a tensile tester (manufactured by Shimadzu Corporation). The results are shown in Table 1.
將關於實施例及比較例之黏晶薄膜於150℃下加熱1小時。接著，將它們分別層合至厚度200μm，得到寬度10mm、初始長度40mm之測定樣品。接著，使用拉伸試驗機島津製作公司製)於拉伸速度300mm/分鐘、10mm之條件25℃下之啦身斷裂伸長率。結果如表1所示。 The die-bonded films of the examples and the comparative examples were heated at 150 ° C for 1 hour. Next, these were laminated to a thickness of 200 μm to obtain a measurement sample having a width of 10 mm and an initial length of 40 mm. Next, the elongation at break of the body at a tensile speed of 300 mm/min and a condition of 10 mm at 25 ° C was used using a tensile tester Shimadzu Corporation. The results are shown in Table 1.
將各實施例及比較例中得到之黏晶薄膜於60℃下黏貼於9.5mm見方之鏡面晶片，將附有鏡面晶片之黏晶薄膜於溫度120℃、壓力0.1MPa、時間1秒之條件下黏晶於BGA基板。接著，利用乾燥機於150℃下實施1小時熱處理。接者，使用成形機(TOWA Press公司製，Manual PressY-1)，於成形溫度175℃、合模壓力184kN，壓鑄壓力5kN，時間120秒之條件下密封步驟。密封步驟後，使用超音波映射裝置(日立高科公司製，FS200II)觀察黏晶薄膜與鏡面晶片之間之空隙。使用二值化軟件(Win Roof ver.5.6)算出觀察圖像中空隙所佔之面積。空隙所佔之面積相對於黏晶薄膜之表面積而言小於10%之情況評估為「○」，為10%以上且小於30%之情況評估為「△”」，為30%以上之情況評估為「×”」。結果如表1所示。 The viscous film obtained in each of the examples and the comparative examples was adhered to a 9.5 mm square mirror wafer at 60 ° C, and the fused crystal film with the mirror wafer was placed at a temperature of 120 ° C, a pressure of 0.1 MPa, and a time of 1 second. Bonded to the BGA substrate. Next, heat treatment was performed at 150 ° C for 1 hour using a dryer. The sealing step was carried out under the conditions of a forming temperature of 175 ° C, a mold clamping pressure of 184 kN, a die casting pressure of 5 kN, and a time of 120 seconds using a molding machine (manufactured by TOWA Press Co., Ltd., Manual Press Y-1). After the sealing step, the gap between the die-bonded film and the mirror wafer was observed using an ultrasonic mapping device (FS200II, manufactured by Hitachi High-Technologies Corporation). The area occupied by the voids in the observed image was calculated using binarization software (Win Roof ver. 5.6). The case where the area occupied by the void is less than 10% with respect to the surface area of the die-bonded film is evaluated as "○", and when it is 10% or more and less than 30%, it is evaluated as "△", and when it is 30% or more, it is evaluated as "X"". The results are shown in Table 1.
將各實施例及比較例中得到之黏晶薄膜於60℃下黏貼於9.5mm見方之鏡面晶片，將附有鏡面晶片之黏晶薄膜於溫度120℃、壓力0.1MPa、時間1秒之條件下黏晶於BGA基板。然後，利用乾燥機150℃下實施1小時熱處理。接著，使用成形機(TOWA Press公司製，Manual PressY-1)，於成形溫度175℃、合模壓力184kN，壓鑄 壓力5kN，時間120秒之條件下進行密封步驟。接著，於175℃進行5小時熱硬化。之後，在溫度30℃、濕度60%RH、時間72小時之條件進行吸濕操作。然後，將樣品通入以260℃以上之溫度保持10秒之方式設定了溫度之IR回流焊爐。對9個鏡面晶片，用超音波顯微鏡觀察於黏晶薄膜與BGA基板之介面是否發生了剝離，算出發生了剝離之比例。結果如表1所示。 The viscous film obtained in each of the examples and the comparative examples was adhered to a 9.5 mm square mirror wafer at 60 ° C, and the fused crystal film with the mirror wafer was placed at a temperature of 120 ° C, a pressure of 0.1 MPa, and a time of 1 second. Bonded to the BGA substrate. Then, heat treatment was performed for 1 hour at 150 ° C using a dryer. Next, using a molding machine (manufactured by TOWA Press Co., Ltd., Manual Press Y-1) at a forming temperature of 175 ° C and a clamping pressure of 184 kN, die casting The sealing step was carried out under the conditions of a pressure of 5 kN and a time of 120 seconds. Next, heat hardening was performed at 175 ° C for 5 hours. Thereafter, the moisture absorption operation was carried out under the conditions of a temperature of 30 ° C, a humidity of 60% RH, and a time of 72 hours. Then, the sample was passed through an IR reflow furnace in which the temperature was set at a temperature of 260 ° C or higher for 10 seconds. For the nine mirror wafers, whether the interface between the die-bonded film and the BGA substrate was peeled off was observed by an ultrasonic microscope, and the ratio of peeling occurred was calculated. The results are shown in Table 1.
10‧‧‧附有切割片之黏晶薄膜 10‧‧‧Current film with dicing sheet
11‧‧‧切割片 11‧‧‧Cut slices
12‧‧‧基材 12‧‧‧Substrate
14‧‧‧黏著劑層 14‧‧‧Adhesive layer
16‧‧‧黏晶薄膜 16‧‧‧Met film
4‧‧‧半導體晶圓 4‧‧‧Semiconductor wafer
16a‧‧‧晶圓黏貼部分 16a‧‧‧ wafer sticking part
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| WO2016158760A1 (en) * | 2015-03-31 | 2016-10-06 | 東レ株式会社 | Resin film for electronic component, resin film for electronic component provided with protective film, and semiconductor device and method for manufacturing same |
| JP6005313B1 (en) * | 2016-02-10 | 2016-10-12 | 古河電気工業株式会社 | Conductive adhesive film and dicing die bonding film using the same |
| JP5972490B1 (en) | 2016-02-10 | 2016-08-17 | 古河電気工業株式会社 | Conductive adhesive composition, and conductive adhesive film and dicing / die bonding film using the same |
| JP5972489B1 (en) | 2016-02-10 | 2016-08-17 | 古河電気工業株式会社 | Conductive adhesive film and dicing die bonding film using the same |
| JP5989928B1 (en) | 2016-02-10 | 2016-09-07 | 古河電気工業株式会社 | Conductive adhesive film and dicing die bonding film using the same |
| JP6005312B1 (en) | 2016-02-10 | 2016-10-12 | 古河電気工業株式会社 | Conductive adhesive film and dicing die bonding film using the same |
| WO2018029744A1 (en) * | 2016-08-08 | 2018-02-15 | 東レ株式会社 | Resin sheet for electronic component, film-protected resin sheet for electronic component, and semiconductor device and production process therefor |
| JP7164299B2 (en) * | 2016-10-31 | 2022-11-01 | 積水化学工業株式会社 | Pressure-sensitive adhesive layer, and adhesive tape and composition using the same |
| JP6961387B2 (en) * | 2017-05-19 | 2021-11-05 | 日東電工株式会社 | Dicing die bond film |
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| JP6977588B2 (en) * | 2018-01-30 | 2021-12-08 | 昭和電工マテリアルズ株式会社 | Manufacturing method of semiconductor devices and adhesive film |
| JP7217175B2 (en) * | 2019-03-01 | 2023-02-02 | 日東電工株式会社 | Semiconductor back adhesion film and dicing tape integrated semiconductor back adhesion film |
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